Herbicidal sulfonamides

ABSTRACT

This invention relates to ortho-(isoxazolyl, isothiazolyl, pyrazolyl, thiadiazolyl, oxadiazolyl, and triazolyl)benzenesulfonamides and their use as herbicides.

RELATED APPLICATION

This application is a division of application Ser. No. 436,631, filedOct. 29, 1982, now U.S. Pat. No. 4,511,392 which is acontinuation-in-part of my application U.S. Ser. No. 337,934, filed Jan.7, 1982, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to ortho-heterocyclicbenzenesulfonamides and,more particularly, to ortho-(isoxazol-3, or 4-, or5-yl)benzenesulfonamides, ortho-(isothiazol-3, or 4-, or5-yl)benzenesulfonamides, ortho-(1H-pyrazol-1, or 3-, or 4-, or5-yl)benzenesulfonamides,ortho-(1,3,4-oxadiazol-2-yl)benzenesulfonamides,ortho-(1,2,4-oxadiazol-3, or 5-yl)benzenesulfonamides,ortho-(1,2,5-oxadiazol-3-yl)benzenesulfonamides,ortho-(1,3,4-thiadiazol-2-yl)benzenesulfonamides,ortho-(1,2,4-thiadiazol-3-, or 5-yl)benzenesulfonamides,ortho-(1,2,5-thiadiazol-3-yl)benzenesulfonamides,ortho-(1,2,3-thiadiazol-4-, or 5-yl)benzenesulfonamides,ortho-(1H-1,3,4-triazol-1-, or 2-yl)benzenesulfonamides,ortho-(1H-1-methyl-1,2,4-triazol-3-, or 5-yl)benzenesulfonamides, orortho-(1H-1,2,4-triazol-1-yl)benzenesulfonamides and their use inagriculturally suitable compositions as pre-emergence and/orpost-emergence herbicides and as plant growth regulants.

DESCRIPTION OF THE PRIOR ART

U.S. Pat. Nos. 4,127,405 and 4,169,719 disclose herbicidalmethoxymethylpyrimidine sulfonylurea compounds of the type which containa --CH₂ OCH₃ heterocyclic substituent.

European Patent Application No. 7687 discloses herbicidal sulfonylureacompounds such as, among others, ##STR1## where

X is CH₃ or OCH₃ ;

Z is CH or N; and

Y is C₁ -C₄ alkyl substituted with OCH₃, OC₂ H₅, CN, C(O)L, or 1-3 atomsof F, Cl, or Br, where L is NH₂, OH, N(OCH₃)CH₃, NH(C₁ -C₄ alkyl), N(C₁-C₄ alkyl) or C₁ -C₆ alkoxy.

U.S. Ser. No. 264,331, now U.S. Pat. No. 4,378,991, issued Apr. 5, 1983discloses herbicidal o-phenylbenzenesulfonylureas.

SUMMARY OF THE INVENTION

This invention relates to ortho-(heterocyclic)benzenesulfonamides ofFormula I and to their agriculturally suitable salts, agriculturalcompositions containing them as an active ingredient, and to theirmethod of use as general or selective pre-emergence and/orpost-emergence herbicides and as plant growth regulants. ##STR2## where

Q is ##STR3## p W" is O or S;

W is O, S or NR;

W' is O or S;

R is H or C₁ -C₄ alkyl;

R₁ is H, F, Cl, Br, CH₃, CF₃ or OCH₃ ;

R₂ is H, CH₃, C₂ H₅, Cl or Br;

R₃ is H, CH₃, C₂ H₅, Cl, Br, OCH₃, OC₂ H₅ or SCH₃ ;

R₄ is H or C₁ -C₄ alkyl;

R₅ is H, CH₃, C₂ H₅, Cl, Br, OCH₃, OC₂ H₅ or SCH₃ ;

R₆ is H, CH₃ or C₂ H₅ ;

R₇ is H or C₁ -C₄ alkyl;

R₁₂ is H or CH₃ ;

R₁₂ ' is H or CH₃ ;

R₁₃ is H or CH₃ ;

R₁₄ is H, CH₃, C₂ H₅, Cl, OCH₃, OC₂ H₅ or SCH₃ ;

R₁₅ is C₁ -C₃ alkyl;

A is ##STR4##

X is CH₃, OCH₃ or Cl;

Y is CH₃, C₂ H₅, CH₂ OCH₃, OCH₃, OC₂ H₅, CH(OCH₃)₂, NH₂, NHCH₃, N(CH₃)₂,OCH₂ CH₂ OCH₃, OCH₂ CF₃, SCH₃, CF₃ or ##STR5##

Z is CH or N;

X₁ is CH₃, OCH₃ or Cl;

G is O or CH₂ ;

X₂ is C₁ -C₃ alkyl or CH₂ CF₃ ;

Y₂ is CH₃ O, C₂ H₅ O, CH₃ S or C₂ H₅ S;

and their agriculturally suitable salts; provided that

(a) when R₂ is Cl or Br, then W is O or S;

(b) when X is Cl, then Z is CH and Y is OCH₃, OC₂ H₅, NH₂, NHCH₃ orN(CH₃)₂ ;

(c) when W" is S, then R₁₃ is H,

A is ##STR6## and Y is CH₃, OCH₃, C₂ H₅, OC₂ H₅, CH₂ OCH₃, ##STR7##

(d) when Q is ##STR8## then one of R₂ or R₃ must be H, CH₃ or C₂ H₅ ;

(e) when Q is ##STR9## then one of R₂ or R₅ must be H, CH₃ or C₂ H₅ ;

(f) the total number of carbon atoms of Q must be less than or equal to8.

Preferred for their higher herbicidal activity and/or their morefavorable ease of synthesis are:

(1) Compounds of Formula I where

R and R₁₅ are independently CH₃ or C₂ H₅ ;

R₂, R₃, R₄, R₅, R₆, R₇ and R₁₄ are independently H or CH₃ ; and

W" is O.

(2) Compounds of the Preferred (1) where R₁ and R₁₃ are H.

(3) Compounds of Preferred (2) where Y is CH₃, CH₂ OCH₃, OCH₃, OC₂ H₅,CH(OCH₃)₂ or ##STR10## and A is ##STR11##

(4) Compounds of preferred (3) where Q is ##STR12##

(5) Compounds of preferred (3) where Q is ##STR13##

(6) Compounds of preferred (3) where Q is ##STR14##

(7) Compounds of preferred (3) where Q is ##STR15##

(8) Compounds of preferred (3) where Q is ##STR16##

(9) Compounds of preferred (3) where Q is ##STR17##

(10) Compounds of preferred (3) where Q is ##STR18##

(11) Compounds of preferred (3) where Q is ##STR19##

(12) Compounds of preferred (3) where Q is ##STR20##

(13) Compounds of preferred (3) where Q is ##STR21##

(14) Compounds of preferred (3) where Q is ##STR22##

(15) Compounds of preferred (3) where Q is ##STR23##

(16) Compounds of preferred (3) where Q is ##STR24##

(17) Compounds of preferred (3) where Q is ##STR25##

(18) Compounds of preferred (3) where Q is ##STR26##

(19) Compounds of preferred (3) where Q is ##STR27##

(20) Compounds of preferred (3) where Q is ##STR28##

(21) Compounds of preferred (3) where Q is ##STR29##

(22) Compounds of preferred (3) where Q is ##STR30##

(23) Compounds of preferred (3) where Q is ##STR31##

(24) Compounds of preferred (3) where Q is ##STR32##

(25) Compounds of preferred (3) where Q is ##STR33##

(26) Compounds of preferred (3) where Q is ##STR34##

(27) Compounds of preferred (3) where Q is ##STR35## and

(28) Compounds of preferred (3) where Q is ##STR36##

Specifically preferred are compounds of the broad scope selected fromthe group consisting of:

2-(isoxazol-5-yl)-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]benzenesulfonamide,m.p. 183°-187°;

2-(isoxazol-5-yl)-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]benzenesulfonamide,m.p. 185°-189°;

N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(1- and/or2-methyl-1H-pyrazol-3-yl)benzenesulfonamide, m.p. 210°-212°;

N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-(1- and/or2-methyl-1H-pyrazol-3-yl)benzenesulfonamide, m.p. 200°-205°;

N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(1-methyl-1H-pyrazol-4-yl)benzenesulfonamide,m.p. 220°-226°;

N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-(1-methyl-1H-pyrazol-4-yl)benzenesulfonamide,m.p. 221°-224°;

N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(isoxazol-4-yl)benzenesulfonamide,m.p. 175°-178°;

2-(isoxazol-4-yl)-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]benzenesulfonamide,m.p. 181°-185°; and

2-(isoxazol-4-yl)-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]benzenesulfonamide,m.p. 178°-181°.

DETAILED DESCRIPTION OF THE INVENTION Synthesis

The compounds of Formula (I) can be prepared by one or more of themethods described below in Equations 1 to 3a.

As shown in Equation 1 below, compounds of Formula (I), where W" is O,can be prepared by reacting a sulfonamide of Formula (II) with anappropriate methyl carbamate of Formula (III) in the presence of anequimolar amount of trimethylaluminum, wherein R₁, R₁₃, Q and A are aspreviously defined. ##STR37##

The reaction of Equation 1 is best run in methylene chloride at about25° to 40° C. for 10 to 96 hours under a nitrogen atmosphere. Theproduct can be isolated by addition of an aqueous acetic acid solutionfollowed by extraction of the product into methylene chloride, or byfiltration of a product of low solubility. The product can be purifiedby trituration with solvents such as 1-chlorobutane, ethyl acetate orethyl ether or by column chromatography on silica gel.

As shown in Equation 1a, many compounds of Formula (I), where W" is O,can also be prepared by reacting a sulfonylcarbamate of Formula (IIa)with an appropriate amine of Formula (VII). ##STR38## wherein

R₁, R₁₃, A and Q are as defined above; except R₃ and R₁₄ are H or C₁ -C₂alkyl,

R₅ is C₁ -C₂ alkyl, and R is C₁ -C₄ alkyl.

The reaction is carried out at 50°-100° C. in a solvent such as dioxanefor 0.5 to 24 hours as taught in EPO Publication No. 44807. The requiredcarbamates IIa are prepared by reacting the corresponding sulfonamide IIwith diphenylcarbonate in the presence of a strong base.

Some of the compounds of Formula (I) can also be prepared as shown inEquation 2 below. ##STR39## wherein

Y' is CH₃ or C₂ H₅ and R₁, Q and Z are as originally defined, except R₃and R₅ are not Cl or Br and R₁₄ is not Cl.

The reactions of Equation 2 are run according to similar procedurestaught in European Patent No. 30,140. Thus, in reaction 2a, asulfonamide of Formula (II) is reacted with a dichloropyrimidinylisocyanate or dichlorotriazinyl isocyanate of Formula (IV) in an inertsolvent such as acetonitrile at reflux for 0.5 to 3 hours to form asulfonylurea of Formula (V). The product is isolated by filtration. Inreaction 2b, V is reacted with two mole equivalents of sodium methoxideor sodium ethoxide in tetrahydrofuran at 0° to 25° C. for about onehour, followed by acidification with hydrochloric acid to a pH of about1, to form a sulfonylurea of Formula (Ia). The product is isolated byfiltration. In reaction 2c, Ia is reacted with two mole equivalents ofsodium methoxide in methanol at 25° to about 50° C. for about 1 hour,followed by acidification with hydrochloric acid to a pH of about 1, toform a sulfonylurea of Formula (Ib). Alternatively, as shown in reaction2d, V can be reacted with at least three mole equivalents of sodiummethoxide at 20° to 50° C. for about 1 hour, followed by acidificationwith hydrochloric acid to a pH of about 1, to provide Ic directly, whereY' of Ib is OCH₃. The products of reactions 2c and 2d are isolated byaddition of water and filtration.

The heterocyclic isocyanates of Formula (IV) in Equation 2 above can beprepared by methods described in Swiss No. 579,062, U.S. Pat. No.3,919,228, U.S. Pat. No. 3,732,223 and Angew Chem. Int. Ed., 10, 402(1976), the disclosures of which are herein incorporated by reference.

As shown in Equation 3 below, some of the compounds of Formula (I),where W" is O, can also be prepared by reacting a sulfonyl isocyanate ofFormula (VI) with an amine of Formula (VII). ##STR40## wherein

R₁, R₁₃, Q and A are as originally defined.

The reaction of Equation 3 above can best be carried out in an inert,aprotic, organic solvent such as methylene chloride, tetrahydrofuran oracetonitrile at ambient pressure and temperature. The mode of additionis not critical; however, it is often convenient to add the sulfonylisocyanate to a stirred suspension of amine VII. The reaction isgenerally exothermic. In some cases, the desired product is insoluble inthe warm reaction medium and crystallizes from it in pure form. Productssoluble in the reaction medium are isolated by evaporation of thesolvent, trituration of the solid residues with solvents such as1-chlorobutane, ethyl ether, ethyl acetate or pentane and filtration.Impure products may be purified by column chromatography on silica gel.

Many of the intermediate sulfonyl isocyanates of Formula (VI) inEquation 3 above can be prepared, although often times in low yields,from sulfonamides by methods described in U.S. Pat. No. 4,238,621. Themethod requires reacting sulfonamides with phosgene, in the presence ofn-butyl isocyanate and a tertiary amine catalyst, at reflux in a solventsuch as xylene. A preferred catalyst is 1,4-diazabicyclo[2.2.2]octane(DABCO).

Alternatively, many of the sulfonyl isocyanates VI can be prepared,although again in low yields, from sulfonamides by a two-step procedure.This consists of (1) reacting the sulfonamide with n-butyl isocyanateand a base such as potassium carbonate at reflux in an inert solventsuch as 2-butanone to form a n-butyl sulfonylurea; and (2) reacting thiscompound with phosgene and DABCO catalyst at reflux in xylene solvent.This method is similar to a procedure taught by Ulrich and Sayigh, NewMethods of Preparative Organic Chemistry, Vol. VI, p. 223-241, AcademicPress, New York and London, W. Foerst Ed.

As shown in Equation 3a below, compounds of Formula (I), where W" is S,can be prepared by reacting sulfonamide II with an appropriate triazineor pyrimidine isothiocyanate of Formula (VIIj). ##STR41## wherein

R₁, Q, X, Y and Z are as originally defined.

The reaction of Equation 3a is carried out by dissolving or suspendingthe sulfonamide and isothiocyanate in a polar solvent such as acetone,acetonitrile, ethyl acetate or methyl ethyl ketone, adding an equivalentof a base such as potassium carbonate and stirring the mixture atambient temperature up to the reflux temperature for one to twenty-fourhours as taught in EPO Publication No. 35,893. The requiredisothiocyanates VIIj are prepared according to the method of JapanPatent Application Pub:Kokai 51-143686, June 5, 1976, or that of W.Abraham and G. Barnikow, Tetrahedron, 29, 691 (1973).

As shown in Equation 4 below, intermediate sulfonamides of Formula (II)described above can be prepared from amines of Formula (VIII) by atwo-step procedure. This consists of (4a) diazotizing VIII and couplingthe diazonium salt with sulfur dioxide to form a sulfonyl chloride ofFormula (IX); and (4b) aminating IX with ammonium hydroxide or anhydrousammonia to form II. ##STR42## wherein

R₁ and Q are as originally defined.

The reaction of Equation 4a is accomplished by treating a solution ofamine VIII in a mixture of concentrated hydrochloric acid and glacialacetic acid with a solution of sodium nitrite in water at -5° to 5° C.After stirring for 10-30 minutes at about 0° C. to insure completediazotization, the solution is added to a mixture of an excess of sulfurdioxide and a catalytic amount of cuprous chloride or cupric chloride inglacial acetic acid at about 10° C. The temperature is kept at about 10°C. for 1/4 to 1 hour, then raised to 20° to 30° C. and held at thattemperature for 2 to about 24 hours. This solution is then poured into alarge excess of ice water. The sulfonyl chloride IX can be isolated byfiltration or by extraction into a solvent such as ethyl ether,methylene chloride or preferably, 1-chlorobutane, followed byevaporation of the solvent.

The amination described in the reaction of Equation 4b above isconveniently carried out by treating a solution of the sulfonyl chlorideIX with at least two mole equivalents of anhydrous ammonia in a solventsuch as ethyl ether or methylene chloride at -20° to 30° C. If thesulfonamide product II is insoluble, it may be isolated by filtrationfollowed by washing out the salts with water. If product II is solublein the reaction solution, it may be isolated by filtering off theprecipitated ammonium chloride and evaporation of the solvent.Alternatively, many sulfonamides II can be prepared by reaction ofcorresponding sulfonyl chlorides IX with excess aqueous ammoniumhydroxide in tetrahydrofuran at 0° to about 40° C. for 0.5 to 10 hours.The sulfonamide product II is isolated by evaporation of thetetrahydrofuran solvent, addition of water to the residue andfiltration.

Alternatively, the intermediate sulfonyl chloride IXa can be prepared asshown below in Equation 4a. ##STR43##

According to Equation 4a, a lithium salt, prepared by reaction of1-(2-bromophenyl)pyrazole with butyl lithium in ether at about -70° C.,is added to sulfuryl chloride in hexane at about -30° to -20° C. andstirred for 0.5 to 10 hours at -30° to 30° C. to yield sulfonyl chlorideIXa, according to teachings of S. N. Bhattacharya et al., J. Chem. Soc.(C), 1265 (1968). Subsequent reaction of IXa with ammonia or ammoniumhydroxide as described above provides the corresponding sulfonamide.

Starting with appropriate ortho-(heterocyclic)bromobenzenes, andcarrying out the procedures described in Equation 4a, or simplemodifications thereof, one skilled in the art may prepare some of theother sulfonyl chlorides of Formula (IX) described above. Of necessity,the reactions are limited to those cases in which the ortho-heterogroup, Q, is inert to lithium reagents under the conditions of thereactions, which will be obvious to one skilled in the art. For ageneral review of metalation with lithium reagents, see H. W. Gschwendand H. R. Rodriguez, Org. Reactions, 26, 1 (1979).

Some of the amines of Formula (VIII) in Equation 4 above are known. Forinstance, 4-(2-aminophenyl)isothiazole may be prepared by the procedureof J. H. Finley, J. Heterocycl. Chem., 6, 841 (1969);2-(2-aminophenyl)-1,3,4-thiadiazole by the procedure of M. Ohta, J.Pharm. Soc. Japan, 73, 701 (1953);2-(2-aminophenyl)-5-methyl-1,3,4-thiadiazole by the procedure of S.Leistner and G. Wagner, Z. Chem., 14, 305 (1974);2-(2-aminophenyl)-1,3,4-oxadiazole by the procedure of M. Vincent etal., Bull. Soc. Chim. France, 1580 (1962);3-(2-aminophenyl)-5-methyl-1,2,4-oxadiazole by the procedure of H.Goncalves et al., Bull. Soc. Chim. France, 2599 (1970);4-(2-aminophenyl)-1,2,4-triazole by the procedure of M. Khan and J.Polya, J. Chem. Soc. C, 85 (1970); and3-methyl-4-(2-aminophenyl)-1,2,4-triazole and3,5-dimethyl-4-(2-aminophenyl)-1,2,4-triazole by the procedure of W.Ried and H. Lohwasser, Justus Liebigs Ann. Chem., 699, 88 (1966).

As shown in Equation 5 below, other amines of Formula (VIII) can beprepared by reduction of corresponding nitrobenzenes of Formula (X) withreagents described below. ##STR44## wherein

R₁ and Q are as originally defined.

The reduction reactions of Equation 5 above can be run by methods knownin the literature by one skilled in the art. For instance, many of thereductions can be run by one or more of the following methods:

(a) with stannous chloride or tin and hydrochloric acid, either neat orin an inert solvent such as methanol, at about 25° to 80° C. for 0.5 to10 hours. For details refer to similar procedures described in G. Corsiet al., Boll. Chim. Farm., 103, 115 (1964); J. H. Finley, J. Heterocycl.Chem., 6, 841 (1969); A. Quilico et al., Gazz. Chim. Ital., 76, 87(1946); and M. Khan and J. Polya, J. Chem. Soc. C., 85 (1970).

(b) with ferrous sulfate heptahydrate and 28% ammonium hydroxide in aninert solvent such as aqueous ethanol at about 40° to 80° C. for about 1to 2 hours. For details refer to similar procedures described in T.Naito et al., Chem. Pharm. Bull., 16, 160 (1968); Neth. Appl. No.6,608,094; and U.S. Pat. No. 3,341,518;

(c) with ammonium chloride and iron powder in an inert solvent such aswater at 50° to about 80° C. for 1 to 3 hours. For details refer to asimilar procedure described in M. Ohta et al., J. Pharm. Soc. Japan, 73,701 (1953);

(d) with sodium hydrogen sulfide in an inert solvent such as methanol atabout 40° to 70° C. for about 0.5 to 1 hour. For details refer tosimilar procedures described in G. Corsi et al., Boll. Chim. Farm., 103,115 (1964); and U.S. Pat. No. 3,270,029;

(e) by catalytic reduction with 5% palladium-on-charcoal, in thepresence of 2 to 5 equivalents of aqueous hydrochloric acid, in an inertsolvent such as ethanol at 25° to 45° C. at 1 to 3 atmospheres ofhydrogen. For details refer to a similar procedure described in U.S.Pat. No. 3,910,942; and Ger. Offen. No. 2,415,978;

(f) by catalytic reduction with 5% Raney Nickel in an inert solvent suchas ethanol or dioxane at 25° to 45° C. at 1 to 3 atmospheres ofhydrogen. For details refer to similar procedures described in U.S. Pat.No. 3,270,029 and Neth. Appl. No. 6,513,932;

(g) by catalytic reduction with 5% palladium-on-charcoal in an inertsolvent such as methanol at 25° to 45° C. at 1 to 3 atmospheres ofhydrogen for short reaction times, i.e., less than 1 hour. For detailsrefer to a similar procedure described in M. Vincent et al., Bull. Soc.Chim. France, 1580 (1962); and,

(h) by reduction with Raney Nickel catalyst and hydrazine hydrate in 95%ethanol at 25° to 80° C. for 0.2 to about 1 hour. For details refer to asimilar procedure described in C. Ainsworth et al., J. Med. Pharm.Chem., 5, 383 (1962).

(i) with sodium sulfide in 50% aqueous p-dioxane at about 25° to 80° C.for 0.25 to 1 hour, or with sodium sulfide and sodium bicarbonate inrefluxing methanol for 1 to 10 hours. For details refer to Y. Lin and S.Lang, Jr., J. Heterocycl. Chem., 17, 1273 (1980) and P. Smith and J.Boyer, J. Am. Chem. Soc., 73, 2626 (1951) respectively; and,

(j) with sodium hydrosulfite in ethanol-water at about 25° to 60° C. for0.25 to 1 hour at a pH of less than 7. For details refer to U.S. Pat.No. 4,229,343.

The ortho-heteroaromatic nitrobenzenes of Formula (X) in Equation 5above are important starting compounds for preparing the compounds I ofthis invention, which can be prepared by the following methods.

As shown in Equation 6 below, certain 5-(2-nitrophenyl)isoxazoles ofFormula (Xa) can be prepared by reacting a 2-nitrophenyl alkyl ketone ofFormula (XI) with an appropriate dimethylalkanamide dimethyl acetal ofFormula (XII) to form a 3-dimethylamino-1-(2-nitrophenyl)-2-propen-1-oneof Formula (XIII). Subsequent reaction of XIII with hydroxylaminehydrochloride provides Xa. ##STR45## wherein

R₁ is as originally defined; and

R₂ and R₃ are H, CH₃ or C₂ H₅.

The reaction of Equation 6a is run at 50° to 140° C. for 3 to 24 hoursin a solvent such as toluene or dimethylformamide or excess dimethylalkanamide dimethyl acetal. The product can be isolated by evaporatingthe solvent. For more details, refer to similar procedures described inTechnical Information Bulletin, "DMF Acetals", Aldrich Chemical,December 1973, and Lin and Lang, J. Org. Chem., 45, 4857 (1980). Thepreparation of dimethyl alkanamide dialkyl acetals is reviewed inAbdulla and Brinkmeyer, Tetrahedron, 35, 1675 (1979).

The reaction of Equation 6b above is run in an inert solvent such asethanol or aqueous dioxane at 25° to 100° C. for 1 to 48 hours. Theproduct is isolated by addition of water and extraction with methylenechloride. For more details refer to similar procedures described in Linand Lang, J. Heterocycl. Chem., 14, 345 (1977).

Another method for preparing some 5-(2-nitrophenyl)isoxazoles is shownin Equation 7 below. The method requires transforming a 2-nitrophenylalkyl ketone of Formula (XI) by a series of procedures to a5-(2-nitrophenyl)-isoxazolin-3-one of Formula (XVI). Subsequent reactionof XVI with phosphorus oxychloride or phosphorus oxybromide provides3-halo-5-(2-nitrophenyl)isoxazoles of Formula (Xa'). Reaction of Xa'with a sodium methoxide, sodium ethoxide or sodium methylmercaptide thenprovides 3-alkoxy or 3-methylthio-5-(2-nitrophenyl)isoxazoles of Formula(Xa"). ##STR46## wherein

R₁ is as originally defined;

R₂ is H, CH₃ or C₂ H₅ ; and

R₃ ' is CH₃ or C₂ H₅.

The 5-(2-nitrophenyl)isoxazolin-3-one of Formula (XVI) in Equation 7above can be prepared by a series of reactions similar to thosedescribed in the art for transforming acetophenone to5-phenylisoxazolin-3-one, e.g., R. Jacquier et al., Bull. Soc. Chim.,3694 (1969) and ibid., 1978 (1970). Thus, by substituting 2-nitrophenylalkyl ketone XI for acetophenone and carrying out the appropriatereactions in the cited art, and which are illustrated in reactions ofEquations 7a to 7c, one skilled in the art can prepare XVI. The reactionof Equation 7d is run in a solvent such as toluene at 50° to 100° C. for0.5 to 3 hours. The product is isolated by evaporation of the solventand purified by column chromatography on silica gel. Reaction 7e is runin a solvent such as methanol or tetrahydrofuran at about 15° to 40° C.for 0.5 to 5 hours. The product is isolated by addition of water andextraction with methylene chloride. The product is purified by columnchromatography on silica gel.

As shown in Equation 8 below, 4-halo-5-(2-nitrophenyl)isoxazoles ofFormula (Xa"") can be prepared by halogenating5-(2-nitrophenyl)isoxazoles of Formula (Xa"') with halogenating reagentsdescribed below. ##STR47## wherein

R₁ and R₃ are as originally defined; and

R₂ is Cl or Br.

The reaction of Equation 8 can be run by one or more of the followingmethods known in the art for halogenating phenylisoxazoles in the4-position of the isoxazole ring in preference to the phenyl ring orother positions of the isoxazole ring:

(a) reacting Xa"' with sulfuryl chloride or sulfuryl bromide at 15° to80° C. for 0.5 to 3 hours, either neat or in a solvent such as methylenechloride or carbon tetrachloride, according to the teachings of J. Carret al., J. Heterocycl. Chem., 20, 934 (1977);

(b) reacting Xa"' with chlorine or bromine at 15° to 60° C. for 0.5 to 5hours in methylene chloride or acetic acid, according to the teachingsof ibid; or

(c) reacting Xa"' with bromine or chlorine and iron powder catalyst in asolvent such as carbon tetrachloride at 25° to 80° C. for 0.5 to 3hours, according to the teachings of N. Kochetkov et al., Zhur.Obshchei. Khim., 28, 359 (1958). The preparation of Xa"' is described inEquations 6 and 7 above.

As shown in Equation 9 below, 4-(2-nitrophenyl)isoxazoles of Formula(Xb) can be prepared by reacting a3-(dimethylamino)-2-(2-nitrophenyl)acrolein of Formula (XVII) withhydroxylamine hydrochloride. ##STR48## wherein

R₁ is as originally defined.

The reaction of Equation 9 is run in ethanol at 25° to 80° C. for 3 to16 hours. The product is isolated by addition of water and extractionwith methylene chloride. The product is purified by recrystallization orcolumn chromatography on silica gel. The starting material XVII isprepared by known methods, e.g., U. Hengartner et al., J. Org. Chem.,44, 3748 (1979).

5-Methyl-4-(2-nitrophenyl)isoxazoles of Formula (Xb') can be prepared asshown in Equation 10 below. The method requires reacting a2-nitrophenylpropanone of Formula (XVIII) with ethyl formate and sodiumethoxide to form a 3-oxo-2-(2-nitrophenyl)butyraldehyde of Formula(XIX). Subsequent reaction of XIX with hydroxylamine provides Xb'.##STR49## wherein

R₁ is as originally defined.

The reaction of Equation 10a is run in ethanol at 0° to about 30° C. forabout 48 hours. The product is isolated by addition of water and 2N HCland extraction with methylene chloride. The reaction of Equation 10b isalso run in ethanol at reflux for about 1 to 10 hours. The product isisolated by addition of water and extraction with methylene chloride.For more details refer to similar procedures described in H. Yasuda,Yakugaku Zasshi, 79, 623 (1959).

As shown in Equation 11 below, 3,5-dimethyl-4-(2-nitrophenyl)isoxazolesof Formula (Xb") can be prepared by reacting a3-(2-nitrophenyl)pentan-2,4-dione of Formula (XX) with hydroxylamine.##STR50## wherein

R₁ is as originally defined.

The reaction of Equation 11 is run in ethanol at 50° to 75° C. for about3 to 10 hours. The product is isolated by addition of water andextraction with methylene chloride. For more details refer to similarprocedures described in Bobranski and Wojtowski, Roczniki Chem., 38,1327 (1964). The starting compounds XX can be prepared by reacting anappropriate 2-halonitrobenzene with the sodium salt of pentan-2,4-dioneby methods obvious to one skilled in the art.

Equation 12 below illustrates a method for preparing3-(2-nitrophenyl)isoxazoles of Formula (Xc). ##STR51## wherein

R₁ is as originally defined; and

R₅ is H, CH₃, C₂ H₅, OCH₃ or OC₂ H₅.

The reaction of Equation 12 is run by procedures similar to those taughtby M. Langella et al., Chim. Ind. (Milan), 47, 996 (1965) for thepreparation of 3-(2-nitrophenyl)isoxazole, and by G. Gaudiano et al.,Gazz. Chim. Ital., 89, 2466 (1959) for the preparation of5-ethoxy-3-(2-nitrophenyl)isoxazole. Thus, a 2-nitrophenylhydroxamicacid chloride of Formula (XXI) is reacted with an appropriate acetylenicGrignard reagent in tetrahydrofuran at 0° to 30° C. for 1 to about 16hours. The product is isolated by addition of water and ammoniumchloride and extraction with methylene chloride. The acetylenic Grignardreagents are prepared from substituted acetylenes by proceduresdescribed in the cited references.

Equation 13 below illustrates a method for preparing3-(2-nitrophenyl)isoxazoles of Formula (Xc'). ##STR52## wherein

R₁ is as originally defined;

R₂ is CH₃ or C₂ H₅ ; and

R₅ is H, CH₃ or C₂ H₅.

The reactions of Equation 13 above can be run by procedures similar tothose described in G. Bianchetti et al., Gazz. Chim. Ital., 93, 1714(1963) for the preparation of various 3-phenylisoxazoles. Thus, inreaction 13a, a 2-nitrophenylhydroxamic acid chloride of Formula (XXI)is reacted with an equimolar amount of triethylamine and aN-alkenylmorpholine of Formula (XXII) in chloroform at reflux for 0.2 toabout 1 hour to form a 5-(N-morpholinyl)-3-(2-nitrophenyl)isoxazoline ofFormula (XXIII). In reaction 13b, XXIII is reacted with 10% hydrochloricacid at reflux for about 0.2 to 0.5 hour to form Xc'. The product Xc' isisolated by extraction with methylene chloride.

Equation 14 below illustrates a method for preparing3-(2-nitrophenyl)isoxazoles of Formula (Xc"). ##STR53## wherein

R₁ is as originally defined; and

R₅ is H, CH₃ or C₂ H₅.

The reactions of Equation 14 above can be run by procedures similar tothose described in R. Micetich, Can. J. Chem., 48, 467 (1970) for thepreparation of various 3-phenylisoxazoles. Thus, in reaction 14a, a2-nitrophenylhydroxamic acid chloride XXI is reacted with equimolaramounts of a vinyl acetate of Formula (XXIV) and triethylamine in asolvent such as ether or tetrahydrofuran at about 30° C. for 1 to 3hours to form a 5-acetoxy-3-(2-nitrophenyl)isoxazoline of Formula (XXV).In reaction 14b, XXV is heated at about 150° to 180° C. for a shortperiod to form Xc".

Equation 15 below illustrates a method for preparing5-halo-3-(2-nitrophenyl)isoxazoles of Formula (Xc"') and 5-alkoxy- or5-methylthio-3-(2-nitrophenyl)isoxazoles of Formula (Xc""). ##STR54##wherein

R₁ is as originally defined;

R₂ is H, CH₃ or C₂ H₅ ; and

R₅ ' is CH₃ or C₂ H₅.

The reactions of Equations 15a and 15b above can be run by proceduressimilar to those described in U.S. Pat. No. 3,781,438 for thepreparation of 5-halo-3-phenylisoxazoles. Thus, in reaction 15a, anethyl 2-(2-nitrobenzoyl)acetate, propionate or butyrate of Formula (XIV)is reacted with hydroxylamine hydrochloride and sodium acetate inethanol at reflux for 0.5 to 5 hours to form a3-(2-nitrophenyl)isoxazolin-5-one of Formula (XXVI). In reaction 15b,XXVI is reacted with an equimolar amount of triethylamine and excessphosphorus oxychloride or phosphorus oxybromide in toluene at 25° to110° C. for 1 to 5 hours to form Xc"'.

The reaction of Equation 15c above can be run by procedures similar tothose described in J. Carr et al., J. Med. Chem., 20, 934 (1977) and R.Micetich et al., Can. J. Chem., 48, 1371 (1970). Thus, Xc"' is reactedwith sodium methoxide, sodium ethoxide or sodium methylmercaptide intetrahydrofuran at 25° to 70° C. for 1 to 16 hours to form (Xc"").

As shown in Equation 16 below, 4-halo-3-(2-nitrophenyl)isoxazoles ofFormula (Xc^(VI)) can be prepared by halogenating3-(2-nitrophenyl)isoxazoles of Formula (Xc^(V)). The reaction is runusing reagents and procedures described above in Equation 8. Thepreparation of Xc^(V) is described above in Equations 12, 14 and 15.##STR55## wherein

R₁ and R₅ are as originally defined; and

R₂ is Cl or Br.

The 5-(2-nitrophenyl)isothiazoles of Formula (Xd) in Equation 17 belowcan be prepared by methods analogous to those described in Yang-i Linand S. A. Lang, J. Org. Chem., 45, 4857 (1980) for the preparation of5-phenylisothiazole. ##STR56## wherein

R₁ is as originally defined; and

R₂ and R₃ are H, CH₃ or C₂ H₅.

According to Equation 17 above, in reaction 17a a3-dimethylamino-1-(2-nitrophenyl)-2-propen-1-one of Formula (XIII) isreacted with phosphorus oxychloride in methylene chloride at 0° to 30°C. for 0.2 to about 2 hours, followed by treatment with sodiumperchlorate in water at 0° to 10° C. for 0.2 to about 1 hour to form aperchlorate salt of Formula (XXVII). In reaction 17b, XXVII is reactedwith sodium sulfide nonahydrate in dimethylformamide and water at 0° to10° C. for 0.2 to about 1 hour to form a3-dimethylamino-1-(2-nitrophenyl)-2-propene-1-thione of Formula(XXVIII). And in reaction 17c, XXVIII is reacted withhydroxylamine-O-sulfonic acid (HSA) and two mole equivalents of pyridinein methanol at 20° to 30° C. for 0.2 to about 1 hour to form Xd. Thepreparation of the starting compounds XIII is described in Equation 6above.

3-Alkoxy-5-(2-nitrophenyl)isothiazoles of Formula (Xd') in Equation 18below can be prepared by methods similar to those described in Ber., 96,944 (1963); German No. 1,193,050 and German No. 1,197,088. The citedreferences describe the preparation of other3-alkoxy-5-phenylisothiazoles. ##STR57## wherein

R₁ is as originally defined;

R₂ is H, CH₃ or C₂ H₅ ; and

R₃ ' is CH₃ or C₂ H₅.

According to Equation 18, in reaction 18a a 2'-cyano-2-nitroacetophenoneof Formula (XXIX) is reacted with methanol or ethanol in a solvent suchas ethyl ether or toluene saturated with hydrogen chloride gas at about0° C. for 1 to 24 hours to form a 2-nitrobenzoylacetamido alkyl ester ofFormula (XXX). In reaction 18b, XXX is reacted with hydrogen sulfide inabsolute methanol or ethanol saturated with hydrogen chloride gas atabout -10° to 25° C. for 1 to 24 hours to form a2-nitrothiobenzoylacetamido alkyl ester of Formula (XXXI). And inreaction 18c, XXXI is reacted with bromine in ethyl acetate containingpyridine at 0° to about 25° C. for about 0.2 to 1 hour to form Xd'.

Equation 19 below illustrates a method for preparing3-halo-5-(2-nitrophenyl)isothiazoles of Formula (Xd") and3-methylthio-5-(2-nitrophenyl)isothiazoles of Formula (Xd"'). ##STR58##wherein

R₁ is as originally defined; and

R₂ is H, CH₃ or C₂ H₅.

The reactions of Equations 19a and 19b above can be run by proceduressimilar to those described in Ber., 96, 944 (1963); German No.1,193,050; and German No. 1,197,088 for the preparation of other3-amino-5-phenylisothiazoles. Thus, in reaction 19a, a2-nitrothiobenzoylacetamido alkyl ester of Formula (XXXI) is reactedwith aqueous 24% NH₄ OH at 15° to 30° C. for 1 to about 12 hours to forma 2-nitrothiobenzoylacetamidine of Formula (XXXII). In reaction 19b,XXXII is reacted with iodine in methanol containing pyridine at 0° toabout 30° C. for about 0.2 to 2 hours to form a3-amino-5-(2-nitrophenyl)isothiazole of Formula (XXXIII).

In the reaction of Equation 19c above, Xd" is prepared from XXXIII viaSandmeyer reactions, according to the teachings of J. Goerdeler and M.Roegler, Chem. Ber., 103, 112 (1970). Thus, XXXIII is reacted withsodium nitrite in concentrated HCl containing Cu₂ Cl₂ and NaCl or inconcentrated HBr containing Cu₂ Br₂ and NaBr at 0° to 30° C. for 0.5 to10 hours to give Xd". And in reaction 19d, Xd" is reacted with sodiummethylmercaptide in tetrahydrofuran at 10° to 60° C. for 0.5 to 5 hoursto form Xd"'. The product is isolated by addition of water andextraction with methylene chloride.

The 4-halo-5-(2-nitrophenyl)isothiazoles of Formula (Xd^(V)) in Equation20 below are prepared by halogenating 5-(2-nitrophenyl)isothiazoles ofFormula (Xd"") with chlorine or bromine in the presence of a base suchas sodium acetate. The reaction is run in acetic acid at 10° to 100° C.for 0.5 to 5 hours. For more details refer to similar proceduresdescribed in the art for halogenating other 5-phenylisothiazoles, e.g.,D. Buttimore et al., J. Chem. Soc., 2032 (1963); T. Naito et al., Chem.Pharm. Bull., 16, 148 (1968); and J. Goerdeler and W. Mittler, Ber., 96,944 (1963). ##STR59## wherein

R₁ and R₃ are as originally defined; and

R₂ is Cl or Br.

The 4-(2-nitrophenyl)isothiazoles of Formula (Xe) in Equation 21 belowcan be prepared by nitrating 4-phenylisothiazoles of Formula (XXXIV)with concentrated nitric acid in concentrated sulfuric acid, accordingto the teachings of J. H. Finley and G. P. Volpp, J. Heterocycl. Chem.,6, 841 (1969). ##STR60## wherein

R₁₂ is H or CH₃.

The reaction of Equation 21 above is run at 0° to 25° C. for 0.5 to 2hours. Following usual work-up the product Xe is purified by columnchromatography on silica gel. The starting compounds XXXIV can beprepared by known methods. Several such methods are described in M.Muehlstaedt, J. Prakt. Chem., 318, 507 (1976); M. Ohashi et al., J.Chem. Soc., 1148 (1970); R. A. Olofson et al., Tetrahedron, 22, 2119(1966); and F. Huebenett et al., Angew Chem., 75, 1189 (1963).

As shown in Equation 22 below, the 3-(2-nitrophenyl)isothiazoles ofFormula (Xf) and (Xf') can be prepared by a series of proceduresstarting from a 2-nitrobenzonitrile of Formula (XXXV). ##STR61## wherein

R₁ is as originally defined; and

R₂ and R₅ are H, CH₃ or C₂ H₅.

The reactions of Equation 22 above can be run by procedures known in theart. Thus, in reaction 22a, 2-nitrobenzonitrile XXXV can be reacted withan appropriate alkyl nitrile and sodium metal in a solvent such as etheror toluene at 0° to 80° C. for about 5 to 25 hours to form a2-imino-2-(2-nitrophenyl)propionitrile of Formula (XXXVI), according tothe teachings of U.S. Pat. No. 3,479,365; Netherlands No. 6,608,094; andT. Naito et al., Bull. Chem. Soc. Japan, 41, 965 (1968).

In the reaction of Equation 22b, XXXVI can be reacted with hydrogensulfide and potassium hydroxide catalyst in methylene chloride at -60°to 80° C. in a sealed tube for 24 to 96 hours to form a2-imino-2-(2-nitrophenyl)thiopropionamide of Formula (XXXVII), accordingto the teachings of T. Naito et al., Chem. Pharm. Bull., 16, 148 (1968)and J. Goerdeler and H. Pohland, Chem. Ber., 94, 2950 (1961).

In the reaction of Equation 22c above, XXXVII can be cyclized byreaction with iodine or bromine in a solvent such as ether, chloroformor ethanol containing potassium carbonate at 20° to 40° C. for 0.5 to 4hours to form a 5-amino-3-(2-nitrophenyl)isothiazole of Formula(XXXVIII), according to the teachings of ibid., Netherlands No.6,608,094 and J. Goerdeler and H. Pohland, Angew Chem., 72, 77 (1962).

In the reaction of Equation 22d above, a diazonium salt, prepared fromXXXVIII and sodium nitrite in sulfuric acid at 0° C. for 0.5 hour, canbe reacted with cuprous oxide and 50% hypophosphorous acid at 0° to 30°C. for about 2 hours to form a 3-(2-nitrophenyl)isothiazole of Formula(Xf), according to the teachings of M. Beringer et al., Helv. Chim.Acta., 49, 2466 (1966).

And in the reaction of Equation 22e above, Xf can be reacted with butyllithium in tetrahydrofuran at -65° C. for about 0.5 hour to form a5-lithio-3-(2-nitrophenyl)isothiazole reagent, according to theteachings of T. Naito et al., Chem. Pharm. Bull., 16, 148 (1968).Subsequent reaction of this reagent with methyl or ethyl iodide, at -65°to 30° C. for 1 to 16 hours, can provide Xf', according to the teachingsof ibid.

The 5-halo-3-(2-nitrophenyl)isothiazoles of Formula (Xf") in Equation 23below can be prepared from 5-amino-3-(2-nitrophenyl)isothiazoles ofFormula (XXXVIII) by Sandmeyer reactions. ##STR62## wherein

R₁ is as originally defined; and

R₂ is H, CH₃ or C₂ H₅.

The reactions of Equation 23 above can be run by procedures similar tothose described in J. Goerdeler and H. Pohland, Chem. Ber., 94, 2950(1961) for the preparation of 5-chloro-3-phenylisothiazole. Thus, inreaction 23a, XXXVIII is diazotized with sodium nitrite in 80%phosphoric acid at -5° to 0° C. for about 0.5 hour. In reaction 23b, thediazonium salt B is reacted with sodium chloride or sodium bromide andcopper sulfate catalyst at 0° to 10° C. for about 1 hour to form Xf".The preparation of XXXVIII is described in Equation 22 above.

The 5-alkoxy- and 5-methylthio-3-(2-nitrophenyl)isothiazoles of Formula(Xf'") in Equation 24 below are prepared by reacting a5-halo-3-(2-nitrophenyl)isothiazole of Formula (Xf") with sodiummethoxide, sodium ethoxide or sodium methylmercaptide. ##STR63## wherein

R₁ is as originally defined;

R₂ is H, CH₃ or C₂ H₅ ; and

R₅ ' is CH₃ or C₂ H₅.

The reaction of Equation 24 is run in a solvent such as methanol,ethanol or tetrahydrofuran at reflux for about 0.5 to 5 hours. Theproduct is isolated by evaporation of solvent, addition of water andfiltration. The reaction of 5-haloisothiazoles with alkoxides orthioalkoxides to form 5-alkoxy- or 5-alkylthioisothiazoles is known inthe art, e.g., K. R. H. Wooldrige, Adv. in Heterocycl. Chem., 14, p. 24(1972).

The 4-halo-3-(2-nitrophenyl)isothiazoles of Formula (Xf^(V)) in Equation25 below are prepared by halogenating 3-(2-nitrophenyl)isothiazoles ofFormula (Xf"") according to procedures described above in Equation 20.The preparation of Xf"" is described above in Equations 22-24. ##STR64##wherein

R₁ and R₅ are as originally defined; and

R₂ is Cl or Br.

Equation 26 below illustrates a method for preparing3-(2-aminophenyl)-1H-pyrazoles of Formula (VIIIa) and5-(2-aminophenyl)-1H-pyrazoles of Formula (VIIIb). ##STR65## wherein

R and R₁ are as originally defined; and

R₂, R₃ and R₅ are H, CH₃ or C₂ H₅.

According to Equation 26 above, in reaction 26a, a 2-acetamidophenylalkyl ketone of Formula (XXXIX) is reacted with a dimethylalkanamidedimethyl acetal of Formula (XL) to form a3-dimethylamino-1-(2-acetamidophenyl)-2-propen-1-one of Formula (XLI).The reaction can be run by procedures described above for the reactionof Equation 6a.

In the reaction of Equation 26b, XLI is reacted with an appropriatehydrazine to form a mixture containing 3-(2-acetamidophenyl)-1H-pyrazoleof Formula (XLII) and 5-(2-acetamidophenyl)-1H-pyrazole of Formula(XLIIa). The reaction is run in ethanol at reflux for 1 to 16 hours. Theproduct mixture is isolated by evaporation of the solvent.

And in the reaction of Equation 26c, amines VIIIa and VIIIb are obtainedby acid hydrolysis of acetamides XLII and XLIIa in the following manner.A mixture containing XLII and XLIIa in concentrated hydrochloric acid isheated at reflux for about 1 hour, cooled and filtered. The solid,composed of hydrochloride salts of VIIIa and VIIIb, is neutralized inwater with 50% NaOH. A mixture containing amines VIIIa and VIIIb isisolated by extraction with methylene chloride. Amines VIIIa and VIIIbmay be separated by high pressure liquid chromatography by one skilledin the art. More preferably, the mixture is reacted directly byprocedures described in Equations 4 and 1 or 2 above to providecorresponding compounds I of the invention as a mixture.

Equation 27 below illustrates a method for preparing5-halo-3-(2-nitrophenyl)-1H-pyrazoles of Formula (Xg) and3-halo-5-(2-nitrophenyl)-1H-pyrazoles of Formula (Xh). ##STR66## wherein

R is C₁ -C₃ alkyl;

R₁ is as originally defined; and

R₂ is H, CH₃ or C₂ H₅.

According to Equation 27 above, in reaction 27a, an ethyl3-(2-nitrophenyl)-3-oxopropanoate of Formula (XIV) is reacted with analkylhydrazine to form a mixture containing a3-(2-nitrophenyl)pyrazolin-5-one of Formula (XLIII) and a5-(2-nitrophenyl)pyrazolin-3-one of Formula (XLIIIa). The reaction isrun in ethanol at reflux for 2 to 16 hours. The product is isolated byaddition of water and extraction with methylene chloride.

And in the reaction of Equation 27b, the mixture containing XLIII andXLIIIa is reacted with phosphorus oxychloride or phosphorus oxybromideto form a mixture containing Xg and Xh. The reaction is run in tolueneat 50° to 100° C. for 0.5 to 5 hours. The product mixture is isolated byevaporation of the solvent and may be purified by column chromatographyon silica gel. The mixture may be separated by high pressure liquidchromatography by one skilled in the art.

Equation 28 below illustrates a method for preparing 5-alkoxy- and5-methylthio-3-(2-nitrophenyl)-1H-pyrazoles of Formula (Xg') and3-alkoxy- and 3-methylthio-5-(2-nitrophenyl)-1H-pyrazoles of Formula(Xh'). ##STR67## wherein

R is C₁ -C₃ alkyl;

R₁ is as originally defined;

R₂ is H, CH₃ or C₂ H₅ ; and

R₃ and R₅ are OCH₃, OC₂ H₅ or SCH₃.

According to Equation 28 above, a mixture containing a5-halo-3-(2-nitrophenyl-1H-pyrazole of Formula (Xg) and a3-halo-5-(2-nitrophenyl)-1H-pyrazole of Formula (Xh) is reacted withsodium methoxide, sodium ethoxide or sodium methylmercaptide to form amixture containing Xg' and Xh'. The reaction is run in a solvent such asmethanol or tetrahydrofuran at 25° to 70° C. for 1 to 10 hours. Theproduct mixture is isolated by addition of water followed by extractionwith methylene chloride. The mixture may be purified by columnchromatography on silica gel. The mixture may be separated by highpressure liquid chromatography by one skilled in the art.

As shown in Equation 29 below, 4-(2-nitrophenyl)-1H-pyrazoles of Formula(Xi) are prepared by reacting a 3-dimethylamino-2-(nitrophenyl)acroleinof Formula (XVII) with an appropriate hydrazine. ##STR68## wherein

R and R₁ are as originally defined.

The reaction of Equation 29 above is run in ethanol at 25° to 80° C. for1 to 10 hours. The product is isolated by evaporation of the solvent andpurified by recrystallization procedures.

As shown in Equation 30 below, a3,5-dimethyl-4-(2-nitrophenyl)-1H-pyrazole of Formula (Xi') is preparedby reacting a 3-(2-nitrophenyl)pentan-2,4-dione of Formula (XX) with anappropriate hydrazine. The reaction can be run by procedures describedabove in Equation 29. ##STR69## wherein

R and R₁ are as originally defined.

A mixture containing 4-(2-nitrophenyl)-1H-pyrazoles of Formula (Xi") and(Xi"') can be prepared by reacting a3-oxo-2-(2-nitrophenyl)butyraldehyde of Formula (XIX) with anappropriate hydrazine, as shown in Equation 31 below. ##STR70## wherein

R and R₁ are as originally defined.

The reaction of Equation 31 above can be run by procedures described inEquation 29 above. The product mixture can be transformed to a mixtureof corresponding compounds I of the invention by a sequence of reactionsdescribed above in Equations 5, 4 and 1 or 2, respectively.

As shown in Equation 32 below, a 1-(2-nitrophenyl)-1H-pyrazole ofFormula (Xj) can be prepared by reacting a 2-nitrophenylhydrazine ofFormula (XLIV) with a 1,3-diketone of Formula (XLV). ##STR71## wherein

R₁ and R₆ are as originally defined; and

R₄ and R₇ are C₁ -C₃ alkyl.

The reaction of Equation 32 is run in a solvent such as tetrahydrofuranor toluene at 25° to 110° C. for 1 to 10 hours. The product is isolatedby evaporation of the solvent and purified by recrystallization orchromatography procedures in the usual manner.1-(2-Nitrophenyl)-1H-pyrazoles of Formula Xj above can also be prepared,where R₄ to R₇ are H, by reacting an appropriate 2-nitrophenylhydrazinewith 1,1,3,3-tetraethoxypropane in ethanol at reflux for about 0.5 to 3hours, according to the teachings of I. Finar and R. Hurlock, J. Chem.Soc., 3024 (1957).

Another methd for preparing 1-(2-nitrophenyl)-1H-pyrazoles isillustrated in Equation 33 below, where R₄ and R₇ can be H as well as C₁-C₃ alkyl. ##STR72## wherein

M is Cl, Br or F; and

R₁ to R₇ are as originally defined.

According to Equation 33, a pyrazole sodium salt of Formula (XLVII) isreacted with a 2-halo-1-nitrobenzene of Formula (XLVI) to form Xj'. Thereaction can be run in an aprotic solvent such as tetrahydrofuran ordimethylformamide at about 0° to 80° C. for 0.5 to 10 hours. The productis isolated in the usual manner by addition of water and extraction withmethylene chloride. The product is purified by recrystallization orchromatography procedures. The sodium salt XLVII is formed by reactingan appropriate pyrazole with sodium hydride in situ by methods known inthe art.

Many 1-(2-nitrophenyl)-1H-pyrazoles of Formula (Xj') above can also beprepared by the Ullmann reaction, according to the teachings of M. Khanand J. Polya, J. Chem. Soc. C., 85 (1970). This requires the reaction ofa 2-halonitrobenzene, such as XLVI above, with an appropriatelysubstituted pyrazole, copper (II) oxide catalyst and potassium carbonatein pyridine at reflux for 0.5 to several hours. The product is purifiedby column chromatography.

The 2-(2-nitrophenyl)-1,3,4-oxadiazoles of Formula (Xk) in Equation 34below can be prepared by reacting a 2-nitrobenzhydrazide of Formula(XLVIII) with excess triethylorthoformate at 100° to 150° C. for 5 to 24hours, according to procedures described in U.S. Pat. No. 3,808,223.##STR73## wherein

R₁ is as originally defined.

The 2-alkyl-5-(2-nitrophenyl)-1,3,4-oxadiazoles of Formula (Xk') inEquation 35 below can be prepared by heating a 2-nitrobenzhydrazide ofFormula (XLIX) in excess phosphorus oxychloride at 70° to 100° C. for0.5 to 2 hours, according to procedures described in ibid. ##STR74##wherein

R₁ is as originally defined; and

R₅ is CH₃ or C₂ H₅.

Equation 36 below illustrates a method for preparing2-methylthio-5-(2-nitrophenyl)-1,3,4-oxadiazoles of Formula (Xk").##STR75## wherein

R₁ is as originally defined.

The reactions of Equation 36 above can be run according to similarprocedures described in E. Hoggarth, J. Chem. Soc., 4811 (1952). Thus,in reaction 36a, 2-nitrobenzhydrazide XLVIII is reacted with carbondisulfide in pyridine solvent at 25° to 80° C. for about 4 to 16 hours,followed by addition of water and acidification with hydrochloric acidto form a 2-mercapto-5-(2-nitrophenyl)-1,3,4-oxadiazole of Formula (L).In reaction 36b, L is reacted with sodium hydroxide and methyl iodide inwater at 0° to 30° C. for 0.2 to 1 hour to form Xk".

Equation 37 below illustrates a method for preparing2-halo-5-(2-nitrophenyl)-1,3,4-oxadiazoles of Formula (Xk"') and2-alkoxy-5-(2-nitrophenyl)-1,3,4-oxadiazoles of Formula (Xk"").##STR76## wherein

R₁ is as originally defined; and

R₅ ' is CH₃ or C₂ H₅.

The reactions of Equation 37 above can be run according to similarprocedures described in U.S. Pat. No. 4,259,104; Golfier and Milcent, J.Heterocycl. Chem., 10, 989 (1973); and R. Madhavan and V. Srinivasan,Indian J. Chem., 7, 760 (1969). Thus, in reaction 37a, a2-nitrobenzhydrazide XLVIII is reacted with phosgene in an aproticsolvent such as benzene at ambient temperature for about 10 hours,followed by addition of two mole equivalents of triethylamine andheating at reflux for about 2 hours to form2-(2-nitriphenyl)-1,3,4-oxadiazolin-5-one of Formula (LI). In reaction37b, LI is reacted with phosphorus pentachloride in phosphorusoxychloride or with phosphorus pentabromide in phosphorus oxybromide at25° to 80° C. for about 5 hours to form (Xk"'). And in reaction 37c,Xk"' is reacted with sodium methoxide or sodium ethoxide in a solventsuch as methanol or tetrahydrofuran at 0° to 30° C. for about 0.5 to 5hours to form Xk"".

The 3-(2-nitrophenyl)-1,2,4-oxadiazoles of Formula (X1) in Equation 38below can be prepared by reacting a 2-nitrobenzamidoxime of Formula(LII) with excess triethylorthoformate at 100° to 150° C. for about 1 to24 hours, according to the teachings of U.S. Pat. No. 3,910,942.##STR77## wherein

R₁ is as originally defined.

The 5-alkyl-3-(2-nitrophenyl)-1,2,4-oxadiazoles of Formula (X1') inEquation 39 below can be prepared by reacting 2-nitrobenzamidoxime LIIwith an appropriate acid chloride in dioxane, with BF₃ ·(C₂ H₅)₂ Ocatalyst, at 25° to 100° C. for about 1 to 18 hours, according to theteachings of ibid., or by reacting LII with acid chloride and pyridinein xylene at 25° to 130° C. for 0.5 to 5 hours, according to theteachings of U.S. Pat. No. 3,270,029. Also, X1' can be prepared byreacting LII with excess anhydride at 100° to 150° C. for 0.5 to 5hours, according to the teachings of ibid. ##STR78## wherein

R₁ is as originally defined; and

R₅ is CH₃ or C₂ H₅.

The 5-methylthio-3-(2-nitrophenyl)-1,2,4-oxadiazoles of Formula (X1") inEquation 40 below can be prepared by reacting 2-nitrobenzamidoxime LIIwith a N,N-pentamethylen-methylmercapto-formamide chloride of Formula(LIII) in N-methylpyrrolidinone at 50° to 80° C. for about 1 to 10hours, according to the teachings of H. Eilingsfeld and L. Moebius,Chem. Ber., 98, 1293 (1965). ##STR79## wherein

R₁ is as originally defined.

Equation 41 below illustrates a method for preparing5-halo-3-(2-nitrophenyl)-1,2,4-oxadiazoles of Formula (X1"') and5-alkoxy-3-(2-nitrophenyl)-1,2,4-oxadiazoles of Formula (X1"").##STR80## wherein

R₁ is as originally defined; and

R₅ ' is CH₃ or C₂ H₅.

The reactions of Equation 41 above can be run by methods known in theart. Thus, in reaction 41a, 2-nitrobenzamidoxime LII is reacted withethyl chloroformate in excess pyridine at 0° to 100° C. for about 1 hourto form a 3-(2-nitrophenyl)-1,2,4-oxadiazolin-5-one of Formula (LIV),according to the teachings of A. R. Katritzky et al., Tetrahedron, 21,1681 (1965). In reaction 41b, LIV is reacted with excess phosphorusoxychloride or phosphorus oxybromide with pyridine catalyst at 25° to100° C. for 1 to 15 hours to form X1"', according to the teachings of T.Fujita et al., Yakagaku Zasshi, 84, 1061 (1964). And in reaction 41c,X1"' is reacted with sodium methoxide or sodium ethoxide in a solventsuch as methanol, ethanol or tetrahydrofuran at 20° to 50° C. for about0.2 to 1 hour to form X1"", according to the teachings of F. Eloy etal., Bull. Soc. Chim. Belg., 78, 47 (1969).

The 5-(2-nitrophenyl)-1,2,4-oxadiazoles of Formula (Xm) in Equation 42below are prepared according to the teachings of Y. Lin et al., J. Org.Chem., 44, 4160 (1979). ##STR81## wherein

R₁ is as originally defined; and

R₅ is H, CH₃ or C₂ H₅.

In the reaction of Equation 42a above, 2-nitrobenzamide LV is reactedwith excess dimethylalkanamide dimethyl acetal at 80° to 120° C. forabout 0.3 to 3 hours to form a N-[(dimethylamino)methylene]benzamide ofFormula (LVI). In reaction 42b, LVI is reacted with hydroxylamine inaqueous dioxane-acetic acid at 25° to 90° C. for 0.5 to 3 hours to formXm.

The 3-alkoxy- and 3-methylthio-5-(2-nitrophenyl)-1,2,4-oxadiazoles ofFormula (Xm') in Equation 43 below are prepared according to theteachings of B. Nash et al., J. Chem. Soc., 2794 (1969). ##STR82##wherein R₁ is as originally defined; and

R₅ ' is CH₃ or C₂ H₅.

Thus, in the reaction of Equation 43a, 2-nitrobenzoyl chloride LVII isreacted with potassium thiocyanate in a solvent such as toluene oracetonitrile at reflux for 0.2 to 5 hours; the resultant benzoylthiocyanate is then reacted with excess methanol, ethanol or methylmercaptan at 25° to 80° C. for 0.2 to 5 hours to form an O-alkylbenzoylthiocarbamate or methyl benzoyldithiocarbamate of Formula(LVIII). In reaction 43b, LVIII is reacted with sodium methoxide andmethyl iodide in methanol at 0° to 25° C. for 1 to 5 hours to form adialkyl benzoyliminothiocarbonate or dimethylbenzoyliminodithiocarbonate of Formula (LIX). And in reaction 43c, LIXis reacted with hydroxylamine in methanol or ethanol at 0° to 25° C. forabout 10 to 96 hours to form Xm'.

Equation 44 below illustrates a method for preparing3-halo-5-(2-nitrophenyl)-1,2,4-oxadiazoles of Formula Xm"'. ##STR83##wherein

R₁ is as originally defined, except R₁ ≠OCH₃.

The reactions of Equation 44 can be run by methods known in the art.Thus, in reaction 44a, 3-merthoxy-1,2,4-oxadiazole Xm" is demethylatedby reaction with excess pyridine.HCl neat at 140° to 160° C. for 0.2 to1 hour under a nitrogen atmosphere to form a5-(2-nitrophenyl)-1,2,4-oxadizolin-3-one of Formula (LX), according tothe teachings of A. Katritzky et al., Tetrahedron, 21, 1681 (1965). Inreaction 44b, LX is reacted with phosphorus oxychloride or phosphorusoxybromide, with pyridine catalyst, at 50° to 100° C. for 1 to 10 hoursto form Xm"', according to the teachings of Eloy and Deryckere, Bull.Soc. Chem. Belg., 78, 41 (1969).

The 3-(2-nitrophenyl)-1,2,5-oxadiazoles of Formula (Xn) in Equation 45below can be prepared by heating a 2-nitrophenylglyoxime of Formula(LXI) with 6N NH₄ OH in an autoclave at 150°-180° C. for 1 to 8 hours,according to the teachings of M. Milone, Gazz. Chim. Ital., 63, 456(1933). ##STR84## wherein

R₁ is as originally defined; and

R₁₄ is H, CH₃ or C₂ H₅.

Equation 46 below illustrates a method for preparing3-halo-4-(2-nitrophenyl)-1,2,5-oxadiazoles of Formula (Xn') and3-alkoxy- and 3-methylthio-4-(2-nitrophenyl)-1,2,5-oxadiazoles ofFormula (Xn"). ##STR85## wherein

R₁ is as originally defined; and

R₁₄ ' is CH₃ or C₂ H₅.

The reactions of Equation 46 above can be run according to similarprocedures described in B. Nash et al., J. Chem. Soc., 2794 (1969).Thus, in reaction 46a, a ω-chloro-(2-nitrophenyl)glyoxime of Formula(LXII) is reacted with phosphorus pentachloride in a solvent such asether or toluene at about 0° to 30° C. for 0.2 to 5 hours to form Xn'.In reaction 46b, Xn' is reacted with sodium methoxide, sodium ethoxideor sodium methylmercaptide in a solvent such as methanol, ethanol ortetrahydrofuran at 25° to 70° C. for 0.5 to 5 hours to form Xn".

The 2-(2-nitrophenyl)-1,3,4-thiadiazoles of Formula (Xo) in Equation 47below can be prepared by reacting 2-nitrothiobenzhydrazide LXIII withexcess triethylorthoformate at reflux for 1 to 16 hours, according tothe teachings of C. Ainsworth, J. Am. Chem. Soc., 77, 1150 (1955).##STR86## wherein

R₁ is as originally defined.

The 2-alkyl-5-(2-nitrophenyl)-1,3,4-thiadiazoles of Formula (Xo') inEquation 48 below can be prepared by reacting 2-nitrothiobenzhydrazideLXIII with an appropriate alkylimidate ester HCl in a solvent such asethanol at 25° to 80° C. for 0.5 to 5 hours, according to the teachingsof H. Weidinger and J. Kranz, Ber., 96, 1059 (1963). ##STR87## wherein

R₁ is as originally defined; and

R₅ is CH₃ or C₂ H₅.

The 2-methylthio-5-(2-nitrophenyl)-1,3,4-thiadiazoles of Formula (Xo")in Equation 49 below can be prepared by cyclizing a methyl3-(2-nitrobenzoyl)dithiocarbazate of Formula (LXIV) in sulfuric acid,polyphosphoric acid, or in benzene with p-toluenesulfonic acid catalyst(p-TsOH), according to the teachings of R. Young and K. Wood, J. Am.Chem. Soc., 77, 400 (1955). ##STR88## wherein

R₁ is as originally defined; and

R₅ ' is CH₃.

Thus, the reaction of Equation 49 above is run in concentrated sulfuricacid at 0° to 30° C. for 0.1 to 0.5 hour. In polyphosphoric acid, thereaction is run at 50° to 90° C. for 1 to 24 hours. And in benzene withp-TsOH catalyst, the reaction is run at reflux for 1 to 24 hours. Thestarting compound LXIV is prepared by alkylation with alkyl iodide ofthe salt formed from an appropriate 2-nitrobenzhydrazide and carbondisulfide in alcoholic potassium hydroxide, according to the method ofM. Busch and M. Starke, J. Prakt. Chem., 93, 49 (1916).

Equation 50 below illustrates a method for preparing2-halo-5-(2-nitrophenyl)-1,3,4-thiadiazoles of Formula (Xo"'). ##STR89##wherein

R₁ is as originally defined.

The reactions of Equation 50 are run by methods known in the art. Thus,in reaction 50a, LXV is cyclized in polyphosphoric acid at 80° to 120°C. for about 0.1 to 1 hour to form a2-amino-5-(2-nitrophenyl)-1,3,4-thiadiazole of Formula (LXVI), accordingto the teachings of E. Hoggarth, J. Chem. Soc., 1163 (1949). In reaction50b, LXVI is transformed to Xo"' by Sandmeyer reactions according tomethods described in J. Goerdeler et al., Chem. Ber., 89, 1534 (1956)and A. Alemagna and T. Bacchetta, Tetrahedron, 24, 3209 (1968). Thisrequires reacting LXVI with sodium nitrite in hydrochloric orhydrobromic acid in the presence of copper powder at 0° to 50° C. for0.2 to 3 hours.

Equation 51 below illustrates a method for preparing2-alkoxy-5-(2-nitrophenyl)-1,3,4-thiadiazoles of Formula (Xo"").##STR90## wherein

R₁ is as originally defined; and

R₅ ' is CH₃ or C₂ H₅.

The reactions of Equation 51 above can be run according to similarprocedures described in K. Doyle and F. Kurzer, Tetrahedron, 32, 1031(1976). Thus, in reaction 51a, a 2-nitrobenzamidrazone.HI of Formula(LXVII) is reacted with an appropriate alkoxythiocarbonylthioacetic acidin 0.5N NaOH at 10° to 30° C. for 0.5 to 2 hours to form aN-(2-nitrobenzimidoyl)-N'-alkoxythiocarbonylhydrazine of Formula(LXVIII). In reaction 51b, LXVIII is cyclized by stirring in 3N HCl at30° to 90° C. for 0.2 to 2 hours to form Xo"". Thealkoxythiocarbonylthioacetic acids are prepared by known methods, e.g.,K. Jensen et al., Acta Chemica. Scand., 23, 1916 (1969).

Equation 52 below illustrates a method for preparing3-(2-nitrophenyl)-1,2,4-thiadiazoles and5-chloro-3-(2-nitrophenyl)-1,2,4-thiadiazoles of Formula (Xp). ##STR91##wherein

R₁ is as originally defined; and

R₅ is H or Cl.

The reaction of Equation 52 can be run according to similar proceduresdescribed in J. Goerdeler et al., Chem. Ber., 53, 8166 (1959); and J.Goerdeler and M. Budnowski, Chem. Ber., 94, 1682 (1961). Thus, a2-nitrobenzamidine.HCl of Formula (LXIX) is reacted withperchloromethylmercaptan or dichloromethanesulfenyl chloride and sodiumhydroxide in a solvent such as water-methylene chloride or aqueousdioxane at about -10° to 10° C. for 0.2 to 10 hours to form Xp.

The 5-bromo-3-(2-nitrophenyl)-1,2,4-thiadiazoles of Formula (Xp') inEquation 53 below can be prepared from5-amino-3-(2-nitrophenyl)-1,2,4-thiadiazoles of Formula (LXX) bySandmeyer reactions, according to the teachings of J. Goerdeler et al.,Chem. Ber., 1534 (1956). ##STR92## wherein

R₁ is as originally defined.

Thus, according to Equation 53, LXX is reacted with sodium nitrite inhydrobromic acid in the presence of copper powder at -10° to 50° C. for0.5 to 3 hours to form Xp'. The starting amine LXX can be prepared byreaction of 5-chloro-3-(2-nitrophenyl)-1,2,4-thiadiazoles Xp, describedabove in Equation 52, with ammonia by standard methods, e.g., F. Kurzer,Adv. in Heterocycl. Chem., 5, 159 (1965).

The 5-alkoxy- and 5-methylthio-3-(2-nitrophenyl)-1,2,4-thiadiazoles ofFormula (Xp") in Equation 54 below can be prepared by reacting5-chloro-3-(2-nitrophenyl)-1,2,4-thiadiazole Xp with sodium methoxide,sodium ethoxide or sodium methylmercaptide in a solvent such asmethanol, ethanol or tetrahydrofuran at 10° to 50° C. for 0.5 to 5hours, according to the teachings of J. Goerdeler et al., Chem. Ber.,90, 182 (1957). ##STR93## wherein

R₁ is as originally defined; and

R₅ ' is CH₃ or C₂ H₅.

Equation 55 below illustrates a method for preparing5-alkyl-3-(2-nitrophenyl)-1,2,4-thiadiazoles of Formula (Xp"').##STR94## wherein

R₁ is as originally defined;

R₅ ' is H or CH₃ ; and

R₅ is CH₃ or C₂ H₅.

The reactions of Equation 55 above can be run according to similarprocedures described in G. Goerdeler and H. Hammer, Ber., 97, 1134(1964). Thus, in reaction 55a,5-chloro-3-(2-nitrophenyl)-1,2,4-thiadiazole Xp is reacted with anappropriate diethyl sodiomalonate in a solvent such as benzene ortetrahydrofuran at reflux for about 5 to 15 hours to form a5-(substituted)-3-(2-nitrophenyl)-1,2,4-thiadiazole of Formula (LXXI).In reaction 55b, LXXI is deesterified by heating it in aqueous sulfuricacid at 90° to 110° C. for about 0.1 to 0.5 hour to form a5-carboxymethylene-3-(2-nitrophenyl)-1,2,4-thiadiazole of Formula(LXXII). And in reaction 55c, LXXII is decarboxylated by heating undernitrogen at about 130° to 150° C. for 0.1 to 1 hour to form Xp"'.

Equation 56 below illustrates a method for preparing5-(2-nitrophenyl)-1,2,4-thiadiazoles of Formula (Xq). ##STR95## wherein

R₁ is as originally defined; and

R₅ is H, CH₃ or C₂ H₅.

The reactions of Equation 56 above can be run according to similarprocedures described in Yang-i Lin et al., J. Org. Chem., 45, 3750(1980). Thus, in reaction 56a, a 2-nitrobenzothioamide of Formula(LXXIII) is reacted with an appropriate N,N-dimethylalkanamide dimethylacetal at 25° to 100° C. for 0.5 to 2 hours to formN-[(dimethylamino)methylene]-2-nitrobenzothioamide of Formula (LXXIV).In the second reaction, LXXIV is reacted withO-(mesitylenesulfonyl)hydroxylamine (MSH) in a solvent such as methylenechloride at 0° to 30° C. for 0.5 to 5 hours to form Xq.

Equation 57 below illustrates a method for preparing3-halo-5-(2-nitrophenyl)-1,2,4-thiadiazoles of Formula (Xq') and3-alkoxy- and 3-methylthio-5-(2-nitrophenyl)-1,2,4-thiadiazoles ofFormula (Xq"). ##STR96## wherein

R₁ is as originally defined; and

R₅ ' is CH₃ or C₂ H₅.

The reactions of Equation 57 above can be run by methods known in theart. Thus, in reaction 57a, a 2-nitrothiobenzoate of Formula (LXXV) isreacted with guanidine in a solvent such as ethanol or tetrahydrofuranat 0° to about 30° C. for 2 to 120 hours to form a2-nitrothiobenzoylguanidine of Formula (LXXVI), according to theteachings of J. Goerdeler and A. Fincke, Chem. Ber., 89, 1033 (1956). Inreaction 57b, LXXVI is cyclized by reaction with bromine in methanol at0° to 60° C. for 0.5 to 3 hours to form a3-amino-5-(2-nitrophenyl)-1,2,4-thiadiazole of Formula (LXXVII),according to the teachings of ibid. In reaction 57c, LXXVII is reactedwith sodium nitrite in hydrochloric acid or hydrobromic acid, in thepresence of copper powder, at -10° to 60° C. for 0.5 to 5 hours to formXq' via Sandmeyer reaction, according to the teachings of F. Kurzer andS. Taylor, J. Chem. Soc., 3234 (1960). And in the last reaction, Xq' isreacted with sodium methoxide, sodium ethoxide or sodiummethylmercaptide in a solvent such as methanol, ethanol ortetrahydrofuran at reflux for 0.5 to 5 hours to form Xq", according tothe teachings of ibid.

The 3-(2-nitrophenyl)-1,2,5-thiadiazoles of Formula (Xr) in Equation 58below can be prepared by nitrating 3-phenyl-1,2,5-thiadiazoles ofFormula (LXXVIII) with nitric acid at 0° to 30° C. for 0.2 to 2 hours,according to the teachings of A. de Munno et al., Int. J. Sulfur Chem.,Part A, 2, 25 (1972). ##STR97## wherein

R₁ is as originally defined; and

R₁₄ is H, Cl or CH₃.

The starting compounds LXXVIII in Equation 58 above can be prepared byknown methods. Several such methods are described in L. Weinstock etal., J. Org. Chem., 32, 2823 (1967); S. Mataka et al., Synthesis, 7, 524(1979); V. Bertini and P. Pino, Angew. Chem. Internat. Edit., 5, 514(1966); and V. Bertini and P. Pino, Corsi. Semin. Chim., 10, 82 (1968).

The 3-alkoxy- and 3-methylthio-4-(2-nitrophenyl)-1,2,5-thiadiazoles ofFormula (Xr') in Equation 59 below can be prepared by reacting3-chloro-4-(2-nitrophenyl)-1,2,5-thiazoles of Formula (Xr) with sodiummethoxide, sodium ethoxide or sodium methylmercaptide in a solvent suchas methanol, ethanol or tetrahydrofuran at about 0° to 60° C. for 0.5 to5 hours, according to the teachings of German No. 1,175,683 and L.Weinstock and P. Pollak, Adv. in Het. Chem., 9, 107 (1968). ##STR98##wherein

R₁ is as originally defined; and

R₁₄ ' is CH₃ or C₂ H₅.

The 4-(2-nitrophenyl)-1,2,3-thiadiazoles of Formula (Xs) in Equation 60below can be prepared according to teachings in U.S. Pat. No. 3,940,407.The method requires reacting an appropriate 2-nitrophenyl alkyl ketonewith ethyl carbazate to form the corresponding hydrazide. Subsequentreaction of the hydrazide with thionyl chloride yields Xs. ##STR99##wherein R₁ and R₆ are as originally defined.

Also, the 5-(2-nitrophenyl)-1,2,3-thiadiazoles of Formula (Xs') inEquation 60a below can be prepared by reacting an appropriate2-nitrophenylacetaldehyde with ethyl carbazate, followed by cyclizingthe hydrazone thus obtained with thionyl chloride according to teachingsin U.S. Pat. No. 3,940,407. ##STR100## wherein R₁ and R₆ are asoriginally defined.

The 1-methyl-5-(2-nitrophenyl)-1H-1,2,4-triazoles of Formula (Xt) inEquation 61 below can be prepared by reacting aN-[(dimethylamino)methylene]-2-nitrobenzamide of Formula (LXXIX) withmethylhydrazine in acetic acid at 50° to 90° C. for 0.5 to 2 hours,according to the teachings of Lin et al., J. Org. Chem., 44, 4160(1979). The starting material LXXIX can be prepared by proceduresdescribed above in the first step of Equation 42. ##STR101## wherein

R₁ and R₆ are as originally defined.

Equation 62 below illustrates a method for preparing1-methyl-3-(2-nitrophenyl)-1H-1,2,4-triazoles of Formula (Xu).##STR102## wherein

R₁ is as originally defined;

R₆ ' is CH₃ or C₂ H₅ ; and

R₆ is H, CH₃ or C₂ H₅.

The reaction of Equation 62 above can be run according to similarprocedures described in M. Atkinson and J. Polya, J. Chem. Soc., 3319(1954). Thus, Xu is prepared by reacting aN-2-nitrobenzimidoyl-N'-methylhydrazine of Formula (LXXX) with formicacid, acetic anhydride or propionic anhydride at about 25° to 100° C.for 0.5 to 1 hour. The starting material LXXX is prepared by reacting anappropriate 2-nitrobenzimidoate HCl with methylhydrazine in pyridine atambient temperature according to the teachings of ibid.

The 1-(2-nitrophenyl)-1H-1,2,4-pyrazoles of Formula Xv in Equation 63below can be prepared by reacting a 1-formyl-2-(2-nitrophenyl)hydrazineof Formula (LXXXI) with excess formamide at reflux for about 1 to 6hours, according to the procedures described in C. Ainsworth et al., J.Med. Pharm. Chem., 5, 383 (1962). ##STR103## wherein

R₁ is as originally defined.

The 1-(2-nitrophenyl)-1H-1,2,4-triazoles of Formula (Xv') in Equation 64below can be prepared by reacting a 2-halo-1-nitrobenzene of Formula(XLVI) with a sodium 1,2,4-triazole salt of Formula (LXXXII). Thereaction can be run by procedures described above in Equation 33 by oneskilled in the art. ##STR104## wherein

M is Cl, Br or F; and

R₁ -R₁₂ are as originally defined.

Many 1-(2-nitrophenyl)-1H-1,2,4-triazoles of Formula (Xv') above canalso be prepared by the Ullman reaction, according to the teachings ofM. Khan and J. Polya, J. Chem. Soc. C., 85 (1970). This requiresreacting a 2-halonitrobenzene, such as XLVI above, with an appropriatelysubstituted 1,2,4-triazole, copper (II) oxide catalyst and potassiumcarbonate in pyridine at reflux for 0.5 to several hours. The product ispurified by column chromatography.

Equation 65 below illustrates a method for preparing4-alkyl-3-(2-nitrophenyl)-4H-1,2,4-triazoles of Formula (Xw). ##STR105##wherein

R₁, R₄ and R₁₅ are as originally defined.

In the reaction of Equation 65a above, a 2-nitrophenyldihydrazidine ofFormula (LXXXIII) can be heated at elevated temperatures, i.e. 100° to200° C., in a solvent such as N-methyl-2-pyrrolidinone to causecyclization to form a 3-(2-nitrophenyl)-4H-1,2,4-triazole of Formula(LXXXIV), according to methods known in the art, e.g., A. Rusanov, Russ.Chem. Rev., 43, 795 (1974). In reaction 65b, LXXXIV can be alkylated toform Xw. This requires reacting LXXXIV with sodium methoxide followed byan appropriate alkyl iodide in methanol at 25° to 100° C. in a sealedtube for 1 to 20 hours. The product is purified by chromatographyprocedures.

The 4-(2-nitrophenyl)-4H-1,2,4-triazoles of Formula (Xx) in Equation 66below can be prepared by reacting a 2-nitroaniline of Formula (LXXXV)with N,N'-diformylhydrazine at 150° to 200° C. for about 0.5 to 2 hours,according to methods known in the art, e.g., C. Ainsworth et al., J.Med. Pharm. Chem., 5, 383 (1962). ##STR106## wherein

R₁ is as originally defined.

Equation 67 below illustrates a method for preparing4-(2-aminophenyl)-4H-1,2,4-triazoles of Formula (VIIIc). ##STR107##wherein

R₁ and R₆ are as originally defined.

The reaction of Equation 67 above is run according to similar proceduresdescribed in W. Ried and H. Lohwasser, Justus Liebigs Ann. Chem., 699,88 (1966) and Angew Chem. Int. Ed. Engl., 5, 835 (1966). Thus,N-(1,1,2-trifluoro-2-chloroethyl)benzimidazole of Formula (LXXXVI) isreacted with excess hydrazine hydrate in ethylene glycol at reflux for 5to 20 hours to form VIIIc.

The heterocyclic amines of Formula (VII) in Equations 1a and 3 are alsoimportant intermediates for the preparation of the compounds of thisinvention, which can be prepared by the following methods.

The pyrimidines and triazines of Formula (VIIa) to (VIId) below areeither known or can be prepared by obvious methods by one skilled in theart. For instance, the synthesis of pyrimidines and triazines of thegeneral formula VIIa has been reviewed in "The Chemistry of HeterocyclicCompounds", a series published by Interscience Publishers, Inc., NewYork and London. 2-Aminopyrimidines are described by D. J. Brown in "ThePyrimidines", Vol. 16 of this series. 2-Amino-1,3,5-triazines arereviewed by E. M. Smolin and L. Rapaport in "s-Triazines andDerivatives", Vol. 13 of the same series. The synthesis of triazines isalso described by F. C. Schaefer, U.S. Pat. No. 3,154,547 and by K. R.Huffman and F. C. Schaefer, J. Org. Chem., 28, 1812 (1963). Thesynthesis of the bicyclic amines VIIc and VIId are described in EPOPublication No. 15,683, and that of VIIb in European Patent PublicationNo. 46,677. ##STR108## wherein

G, X, X₁, Y and Z are as originally defined except Y≠CH(OCH₃)₂ or##STR109##

Pyrimidines below of Formula (VIIe), where Y is CH(OC₂ H₅)₂, aredescribed by W. Braker et al., J. Am. Chem. Soc., 69, 3072 (1947), thedisclosure of which is herein incorporated by reference. Usingtechniques taught by Braker, or suitable modifications that would beobvious to one skilled in the art, the pyrimidines VIIe can be prepared.##STR110## wherein

X is CH₃, OCH₃ or Cl; and

Y is CH(OCH₃)₂ or ##STR111##

Triazines of Formula (VIIf) may be prepared according to the methodsoutlined in Equations 68 and 69. ##STR112## wherein

X is CH₃ or OCH₃ ; and

Y is CH(OCH₃)₂ or ##STR113## wherein

X and Y are as defined in Equation 68.

The reaction of Equation 68a is carried out according to the teachingsof J. M. McElvain and R. L. Clarke, J. Amer. Chem. Soc., 69, 2657(1947), in which the preparation of ethyl diethoxyiminoacetate isdescribed. The intermediate N-cyanoimidate of Formula (LXXXIX) may beprepared according to the teaching of D. Lwowski in Synthesis, 1971,263, by reacting LXXXVIII with cyanamide at pH 5.5, and this may becondensed according to reaction 68c with either acetamidine or O-methylisourea in an alcoholic solvent at 25° to 80° C. to provide theappropriate triazines. Alternatively, the reaction of Equation 69a,described for substituted acetonitriles by F. C. Schaefer and G. A.Peters in J. Org. Chem., 26, 412 (1961), may be used to convert nitrileof Formula (LXXXVII) to the corresponding iminoester. The free base maybe carried on through reactions 69b and 69c, or, alternatively,converted to the amidinium hydrochloride salt (XC) as described in theaforementioned reference, and condensed with either methylN-cyanoacetimidate or with dimethyl N-cyano imidocarbonate in thepresence of one equivalent of sodium methoxide to provide the triazinesof Formula (VIIf).

Cyclic acetals of Formula (VIIh) may also be prepared from compounds ofFormula (VIIg) according to Equation 70 by acetal exchange. ##STR114##wherein

X is CH₃ or OCH₃ ; and

Z is CH or N.

The reaction of Equation 70 is carried out by heating the acyclic acetalin an inert solvent in the presence of one equivalent ethylene glycoland slightly more than one equivalent of a strong acid, such asp-toluenesulfonic acid with removal of the methanol or ethanol formed inthe reaction by distillation. The product is isolated by treatment withaqueous base, and extraction with an organic solvent, and purified bycrystallization or column chromatography.

Preparations of 3-amino-1,2,4-triazoles of Formula (VII) in Equations 1aand 3 are known in the art and 1,2,4-triazoles are reviewed in TheChemistry of Heterocyclic Compounds "Triazoles 1,2,4" (John Wiley andSons, New York, 1981). Commonly used starting materials containingnitrogen are N-aminoguanidine, hydrazine, alkylhydrazines, cyanamide,ethyl cyanoacetimidate, dimethyl cyanodithioimidocarbonate, dimethylcyanoimidocarbonate, ethoxymethylenecyanamide, and acylhydrazines. Someliterature synthesis are illustrated below. Using these techniques orsuitable modifications that would be apparent to one skilled in the art,the 3-amino-1,2,4-triazole intermediates can be readily prepared.

Heating equimolar amounts of ethyl propionimidate hydrochloride andN-aminoguanidine nitrate in pyridine gives 3-amino-5-ethyltriazole;German Patent No. 1,073,499 (1960); Berichte, 96, 1064 (1963).##STR115## Condensation of hydrazine with ethyl N-cyanoacetimidateyields 3-amino-5-methyltriazole; Journal of Organic Chemistry, 28, 1816(1963). ##STR116## U.S. Pat. No. 2,835,581 (1958) teaches thepreparation of 3-amino-5-(hydroxymethyl)triazole from N-aminoguanidineand glycolic acid and British Patent No. 736,568 (1955) describes thesynthesis of 3-amino-5-mercaptotriazole. ##STR117## Condensing hydrazinewith dimethyl cyanodithioimidocarbonate in acetonitrile gives3-amino-5-methylthio-1,2,4-triazole while reaction of hydrazine withdimethyl N-cyanoimidocarbonate produces3-amino-5-methoxy-1,2,4-triazole; Journal of Organic Chemistry, 39, 1522(1974). ##STR118##

Reaction of substituted hydrazines with N-cyanothioimidocarbonates(prepared according to the procedure given in D. M. Wieland, Ph.D.Thesis, 1971, pp. 123-124) yields disubstituted aminotriazoles as shownbelow. ##STR119##

Many of the aminoheterocyclic intermediates of Formula (VII) where R₁₃is methyl may be prepared by a two-step procedure as described for VIIiin Equation 71. ##STR120## wherein

X, Y and Z are as originally defined and

R₁₃ is CH₃.

A solution of the amine (XCI) in concentrated hydrochloric acid istreated with sodium nitrite solution and the chloro compound (XCII) isisolated in the usual manner by filtration of the acidic solution. Arepresentative procedure is described by Bee and Rose in J. Chem. Soc.C, 2031 (1966), for the case in which Z=CH, and X=Y=OCH₃. Displacementof the chlorine of (XCII) may be accomplished by heating with an excessof methylamine in water to obtain the methylamino heterocycle (VIIi).

Equation 72 below illustrates the preparation of the required methylpyrimidinyl carbamates and methyl triazinyl carbamates of Formula (III)in Equation 1. By obvious modifications, other methyl carbamates ofFormula (III) may be prepared by this method by one skilled in the art.##STR121## wherein

X, Y, Z and R₁₃ are as originally defined.

According to Equation 72, a heterocyclic amine is reacted with twoequivalents of sodium hydride and excess dimethyl carbonate to formIIIa. The reaction is run in an inert solvent such as tetrahydrofuran at25° C. to reflux for 1 to 24 hours. The product is isolated by (a)adding about two equivalents of concentrated hydrochloric acid undernitrogen at 0° to 30° C.; (b) filtering; and (c) separating out theorganic phase, then drying (sodium sulfate and/or magnesium sulfate) andconcentrating to dryness in vacuo. The product IIIa may be purifiedfurther by recrystallization or chromatography procedures.

Agriculturally suitable salts of compounds of Formula I are also usefulherbicides and can be prepared in a number of ways known to the art. Forexample, metal salts can be made by contacting compounds of Formula Iwith a solution of an alkali or alkaline earth metal salt having asufficiently basic anion (e.g., hydroxide, alkoxide, carbonate orhydroxide). Quaternary amine salts can be made by similar techniques.

Salts of compounds of Formula I can also be prepared by exchange of onecation to another. Cationic exchange can be effected by direct treatmentof an aqueous solution of a salt of a compound of Formula I (e.g.,alkali metal or quaternary amine salt) with a solution containing thecation to be exchanged. This method is most effective when the desiredsalt containing the exchanged cation is insoluble in water, e.g., acopper salt, and can be separated by filtration.

Exchange may also be effected by passing an aqueous solution of a saltof a compound of Formula I (e.g., an alkali metal or quaternary aminesalt) through a column packed with a cation exchange resin containingthe cation to be exchanged. In this method, the cation of the resin isexchanged for that of the original salt and the desired product iseluted from the column. This method is particularly useful when thedesired salt is water-soluble, e.g., a potassium, sodium or calciumsalt.

Acid addition salts, useful in this invention, can be obtained byreacting a compound of Formula I with a suitable acid, e.g.,p-toluenesulfonic acid, trichloroacetic acid or the like.

The compounds of this invention and their preparation are furtherillustrated by the following examples wherein temperatures are given indegrees centigrade and all parts are by weight unless otherwiseindicated.

EXAMPLE 1 3-(Dimethylamino)-1-(2-nitrophenyl)-2-propen-1-one

To a solution of 126 g of 2-nitroacetophenone in 125 ml of toluene wasslowly added 119 g of N,N-dimethylformamide dimethyl acetal. Thesolution was refluxed for 16 hours, then concentrated to dryness invacuo. The solid residue was washed 1×200 ml of 2-propanol and 2×200 mlof hexane to yield 147 g of the title compound; m.p. 118°-121° C.

Anal. Calcd. for C₁₁ H₁₂ N₂ O₃ : C, 59.9; H, 5.5; N, 12.7. Found: C,59.4; H, 5.5; N, 12.6.

EXAMPLE 2 5-(2-Nitrophenyl)isoxazole

A suspension containing 99 g of3-(dimethylamino)-1-(2-nitrophenyl)-2-propen-1-one, prepared in Example1, and 63 g of hydroxylamine hydrochloride in 250 ml of ethanol wasrefluxed for 16 hours, then concentrated to dryness in vacuo. Water (400ml) was added to the residue, and the resulting suspension was filtered.The solid was recrystallized from 2-propanol to give 60 g of the titlecompound; m.p. 66°-69° C.

Anal. Calcd. for C₉ H₆ N₂ O₃ : C, 56.8; H, 3.2; N, 14.7. Found: C, 56.3;H, 3.3; N, 14.6.

EXAMPLE 3 5-(2-Aminophenyl)isoxazole

To a suspension containing 206 g of stannous chloride dihydrate in 520ml of concentrated hydrochloric acid was cautiously added 56 g of5-(2-nitrophenyl)isozazole, prepared in Example 2. The resultingsuspension was refluxed on a steam bath for about 1 hour, then cooled to10° C. and filtered. The solid was added to about 600 ml of ice-water,and the suspension was made basic to a pH of about 10 with addition of50% NaOH. The aqueous mixture was extracted with methylene chloride.After drying the methylene chloride extract over sodium sulfate, thesolvent was evaporated under reduced pressure to give 32 g of the titlecompound as an oil.

Anal. Calcd. for C₉ H₈ N₂ O: C, 67.5; H, 5.1; N, 17.5. Found: C, 67.1;H, 5.1; N, 17.3.

EXAMPLE 4 2-(Isoxazol-5-yl)benzenesulfonyl chloride

A diazonium salt was prepared by adding a solution of 14.5 g of sodiumnitrite in 30 ml of water to a suspension of 32 g of5-(2-aminophenyl)isoxazole, prepared in Example 3, and 72 ml ofconcentrated hydrochloric acid in 210 ml of glacial acetic acid cooledat 0° to 5° C. After stirring about 0.4 hour, the diazonium saltsuspension was poured in one portion into a mixture consisting of 150 mlof acetic acid, 8.4 g of cupric chloride dihydrate and 60 ml of sulfurdioxide and cooled at 10° C. by an ice-water bath. The mixture wasstirred at 10° to 15° C. for 0.2 hour then at about 20° to 30° C. for 3hours. The suspension was poured into ice-water (about 700 ml) andstirred to form a solid. The mixture was filtered and the solid waswashed 3×100 ml of water and suction dried to give 37 g of crude2-(isoxazol-5-yl)benzenesulfonyl chloride; m.p. 63°-65° C.

EXAMPLE 5 2-(Isoxazol-5-yl)benzenesulfonamide

A solution of 37 g of 2-(isoxazol-5-yl)benzenesulfonyl chloride,prepared in Example 4, in 200 ml of tetrahydrofuran, was cooled in anice-water bath while about 40 ml of concentrated aqueous ammoniumhydroxide was added slowly at 10° to 30° C. The resulting suspension wasstirred at room temperature for 4 hours, then the solvent was evaporatedunder reduced pressure. The residue was stirred in 150 ml of water for0.5 hour, the filtered. The crude, wet solid was dissolved intetrahydrofuran and dried over sodium sulfate. The solid wasrecrystallized from 2-propanol to give 20 g of the title compound; m.p.132°-135° C.

Anal. Calcd. for C₉ H₈ N₂ O₃ S: C, 48.1; H, 3.6; N, 12.5. Found: C,47.9; H, 3.6; N, 12.5.

EXAMPLE 6 N-(Butylaminocarbonyl)-2-(isoxazol-5-yl)benzenesulfonamide

A solution of 8.7 g of 2-(isoxazol-5-yl)benzenesulfonamide prepared inExample 5, 4.7 g of n-butyl isocyanate and 5.4 g of potassium carbonatein 125 ml of 2-butanone was refluxed for 7 hours. The resultingsuspension was concentrated to dryness in vacuo. The residue was takenup in 200 ml of water and extracted once with 100 ml of ethyl ether. Theaqueous layer was acidified with 2N HCl and the resulting suspension wasextracted with methylene chloride. After drying the methylene chlorideextract over sodium sulfate, the solvent was evaporated off underreduced pressure. The solid residue was recrystallized from acetonitrileto give 10 g of the title compound; m.p. 110°-113° C.

Anal. Calcd. for C₁₄ H₁₇ N₃ O₄ S: C, 51.9; H, 5.3; N, 12.9. Found: C,51.2; H, 5.3; N, 12.6.

EXAMPLE 7 2-(Isoxazol-5-yl)benzenesulfonyl isocyanate

A suspension of 6 g ofN-(butylaminocarbonyl)-2-(isoxazol-5-yl)benzenesulfonamide, prepared inExample 6, in 50 ml of xylene containing 0.2 g of DABCO was heated at130°-135° C. while 1.6 ml of phosgene was added portionwise at a rate tomaintain a reflux temperature of 130°-135° C. The mixture was refluxedfor an additional 2 hours, cooled under nitrogen to room temperature,filtered, and the filtrate was concentrated to dryness in vacuo. Asample of the crude oily product displayed a characteristic sulfonylisocyanate band in the IR at 2200 cm⁻¹.

EXAMPLE 8N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(isoxazol-5-yl)benzenesulfonamide

To a suspension of 2.5 g of 2-amino-4,6-dimethoxypyrimidine in 25 ml ofacetonitrile was added 4 g of crude 2-(isoxazol-5-yl)benzenesulfonylisocyanate prepared in Example 7. The resulting suspension was warmed at40° C. for about 3 minutes to form a solution. The solution was stirredat room temperature for 10 hours, then concentrated in vacuo to give aviscous oil. The oil was chromatographed in a dry column of silica gelwith ethyl acetate as eluant. The first fraction from the column wasconcentrated in vacuo to yield a solid. The solid was washed 1×10 ml ofacetonitrile and suction dried to yield 0.5 g of the title compound;m.p. 183°-187° C. The IR spectrum showed a carbonyl absorption at 1710cm⁻¹ indicative of a sulfonylurea.

Anal. Calcd. for C₁₆ H₁₅ N₅ O₆ S: C, 47.4; H, 3.7. Found: C, 47.1; H,3.9.

EXAMPLE 9 Methyl(4,6-dimethoxypyrimidin-2-yl)carbamate

2-Amino-4,6-dimethoxypyrimidine (56 g) was added portionwise to 50%sodium hydride (42.8 g) in 1000 ml of dry tetrahydrofuran. Afterstirring for 0.5 hour, dimethylcarbonate (58.5 g) was added dropwisewith cooling. The mixture was stirred under nitrogen for about 16 hoursat ambient temperature. Concentrated HCl (80 ml) was added slowly asexternal cooling was used to maintain a pot temperature of about 25° C.Saturated aqueous sodium chloride (80 ml) was then added. The solventswere decanted from the precipitated solids and dried over sodiumsulfate. Filtering and evaporating the solvents afforded the crudematerial which was recrystallized from hexane to yield 54 g of the titlecompound, m.p. 81°-83° C. The IR spectrum showed characteristicabsorption bands at 3400 and 1760 cm⁻¹.

EXAMPLE 10 4-(2-Nitrophenyl)isoxazole

A suspension of 75 g of 3-(dimethylamino)-2-(2-nitrophenyl)acrolein[prepared by the procedure of U. Hengartner et al., J. Org. Chem., 44,3748 (1979)] and 47.3 g of hydroxylamine hydrochloride in 300 ml ofethanol was refluxed for 10 hours, then concentrated to dryness invacuo. Water (400 ml) was added to the residue and the suspensionfiltered. The isolated solid was recrystallized from 2-propanol to yield56 g of the title compound; m.p. 51°-54° C.

Anal. Calcd. for C₉ H₆ N₂ O₃ : C, 56.8; H, 3.2; N, 14.7. Found: C, 56.6;H, 3.1; N, 14.4.

EXAMPLE 11 4-(2-Aminophenyl)isoxazole

To a suspension of 108 g of stannous chloride dihydrate in 270 ml ofconcentrated hydrochloric acid was added portionwise 30 g of4-(2-nitrophenyl)isoxazole prepared in Example 10 at less than 30° C.The suspension was stirred at about 20°-35° C. for 10 hours, then cooledto 10° C. and filtered. The solid was added to ice-water (400 ml), 50%NaOH was added to make the suspension basic to a pH of about 10, and theresultant suspension filtered. The solid was washed 3×100 ml of waterand suction dried to give 18 g of the title compound; m.p. 48°-51° C.

Anal. Calcd. for C₉ H₈ N₂ O: C, 67.5; H, 5.1; N, 17.5. Found: C, 67.1;H, 5.1; N, 17.2.

EXAMPLE 12 2-(Isoxazol-4-yl)benzenesulfonyl chloride

By the procedure of Example 4, a diazonium salt was prepared by reacting12 g of 4-(2-aminophenyl)isoxazole prepared in Example 11 with 5.5 g ofsodium nitrite and 27 ml of concentrated hydrochloric acid in 80 ml ofglacial acetic acid. The diazonium salt suspension was added to asuspension of 3.2 cupric chloride dihydrate and 23 ml of sulfur dioxidein 57 ml of glacial acetic acid to give, after addition of excess waterand filtration and suction drying, 15 g of the title compound as a crudesolid; m.p. 100°-104° C.

EXAMPLE 13 2-(Isoxazol-4-yl)benzenesulfonamide

By the procedure of Example 5, 15 g of 2-(isoxazol-4-yl)benzenesulfonylchloride prepared in Example 12 was reacted with 30 ml of concentratedammonium hydroxide in 150 ml of tetrahydrofuran to give, afterrecrystallization from 2-propanol, 11 g of the title compound; m.p.165°-167° C.

Anal. Calcd. for C₉ H₈ N₂ O₃ S: C, 48.2; H, 3.6; N, 12.5. Found: C,47.8; H, 3.7; N, 12.7.

EXAMPLE 14N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(isoxazol-4-yl)benzenesulfonamide

A solution of 2 g of 2-(isoxazol-4-yl)benzenesulfonamide, prepared inExample 13, in 100 ml of methylene chloride was purged with nitrogen. Tothe solution was added carefully 0.8 g of trimethylaluminum (5.5 ml of2M solution in toluene) while cooling the flask at 15° to 30° C. Afterstirring about 0.2 hour, 1.9 g of methyl(4,6-dimethoxypyrimidin-2-yl)carbamate, prepared in Example 9, was addedand the suspension was refluxed for 20 hours under a nitrogenatmosphere. The suspension was cooled in an ice-water bath while 50 mlof 25% aqueous acetic acid was carefully added. Excess water was addedand the organic phase was separated and dried over sodium sulfate. Afterevaporation of the solvent in vacuo, the residue was triturated with 25ml of ethyl acetate to give 0.5 g of the title compound; m.p. 175°-178°C.

Anal. Calcd. for C₁₆ H₁₅ N₅ O₆ S: C, 47.4; H, 3.7; N, 17.3. Found: C,46.8; H, 3.7; N, 17.2.

EXAMPLE 15N-[(4,6-Dichloro-1,3,5-triazin-2-yl)aminocarbonyl]-2-(isoxazol-4-yl)benzenesulfonamide

To 4.5 g of 2-(isoxazol-4-yl)benzenesulfonamide prepared in Example 13in 20 ml of acetonitrile is added 4 g of dichloro-5-triazinylisocyanate. The mixture is refluxed for 2 hours, then is cooled to roomtemperature and filtered. The resulting solid is washed with diethylether to giveN-[(4,6-dichloro-1,3,5-triazin-2-yl)aminocarbonyl]-2-(isoxazol-4-yl)benzenesulfonamide.

EXAMPLE 16N-[(4,6-Dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-2-(isoxazol-4-yl)benzenesulfonamide

To 1 g of sulfonamide prepared in Example 15 in 10 ml of methanol isadded portionwise 0.41 g of sodium methoxide. After an initial exotherm,the suspension is stirred at 25° to 50° C. for about 1 hour, then cooledto room temperature and diluted with excess water (about 30 ml). Thesolution is acidified to a pH of about 1 with concentrated HCl. Theresulting mixture is filtered and suction dried to give the titlecompound.

EXAMPLE 17 1-Methyl-4-(2-nitrophenyl)-1H-pyrazole

A solution of 60 g of 3-(dimethylamino)-2-(2-nitrophenyl)acrolein (seeExample 10) and 16.1 g of methylhydrazine in 200 ml of toluene wasrefluxed for 10 hours, then concentrated to dryness in vacuo. Theresidue was recrystallized from 1-chlorobutane/hexane (about 1:1) toyield 51 g of the title compound; m.p. 41°-44° C.

EXAMPLE 18 1-Methyl-4-(2-aminophenyl)-1H-pyrazole

By the procedure of Example 3, 25 g of1-methyl-4-(2-nitrophenyl)-1H-pyrazole prepared in Example 17 wasreacted with 81.2 g of stannous chloride dihydrate in 200 mlconcentrated HCl at reflux for 1 hour to yield, after similar work up,18 g of the title compound as an oil.

Anal. Calcd. for: C₁₀ H₁₁ N₃ : C, 69.3; H, 6.4; N, 24.2. Found: C, 68.8;H, 6.2; N, 23.9.

EXAMPLE 19 2-(1-Methyl-1H-pyrazol-4-yl)benzenesulfonamide

By the procedure of Example 4, 17.3 g of1-methyl-4-(2-aminophenyl)-1H-pyrazole prepared in Example 18 wasdiazotized with 7.2 g of sodium nitrite and 36 ml of concentrated HCl in104 ml of glacial acetic acid. The diazonium salt suspension was addedto a suspension containing 4.3 g of cupric chloide dihydrate, 30 ml ofsulfur dioxide and 76 ml of acetic acid. After completion of thereaction and addition of water, the suspension was extracted with1-chlorobutane. The extraction was dried over sodium sulfate andconcentrated in vacuo at less than 40° C. to yield 22 g of crude2-(1-methyl-1H-pyrazol-4-yl)benzenesulfonyl chloride as an oil.

By the procedure of Example 5, 21 g of the above oil was reacted with 30ml of concentrated NH₄ OH in 150 ml of tetrahydrofuran to yield a solid.The solid was recrystallized from acetonitrile to yield 17 g of2-(1-methyl-1H-pyrazol-4-yl)benzenesulfonamide; m.p. 183°-186° C.

Anal. Calcd. for C₁₀ H₁₁ N₃ O₂ S: C, 50.6 H, 4.7; N, 17.7. Found: C,50.8; H, 4.7; N, 18.0.

EXAMPLE 20N-[(4-Methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-(1-methyl-1H-pyrazol-4-yl)benzenesulfonamide

By the procedure of Example 14, 2 g of2-(1-methyl-1H-pyrazol-4-yl)benzenesulfonamide, prepared in Example 19,was reacted in 100 ml of methylene chloride with 0.7 g oftrimethylaluminum (5 ml of 2M toluene solution) followed by 1.7 g ofmethyl (4-methoxy-6-methyl-1,3,5-triazin-2-yl)carbamate. After work upand evaporation of the methylene chloride solvent, the residue wastriturated with ethyl acetate to yield 0.6 g of the title compound; m.p.221°-224° C. The IR spectrum showed a carbonyl absorption at 1700 cm⁻¹indicative for a sulfonylurea.

EXAMPLE 21 N-[2-[3-(Dimethylamino)-1-oxo-2-propenyl]phenyl]acetamide

A suspension of 48 g of N-[2-(1-oxo-1-ethanyl)phenyl]acetamide and 38 gof N,N-dimethylformamide dimethyl acetal in 150 ml of toluene was heatedat reflux for about 16 hours, then concentrated in vacuo to a solid. Thesolid was recrystallized from 1-chlorobutane to yield 40 g of the titlecompound; m.p. 90°-95° C.

Anal. Calcd. for C₁₃ H₁₆ N₂ O₂ : C, 67.2; H, 6.9; N, 12.0. Found: C,66.8; H, 6.8; N, 11.7.

EXAMPLE 22 N-[2-(1- and/or 2-methyl-1H-pyrazol-3-yl)phenyl]acetamide

A suspension of 40 g ofN-[2-[3-(dimethylamino)-1-oxo-2-propenyl]phenyl]acetamide prepared inExample 21 and 9.2 g of methylhydrazine in 130 ml of ethanol was heatedat reflux for 10 hours, then concentrated in vacuo. The residue wasrecrystallized from 1-chlorobutane to yield 30 g of the title compound;m.p. 102°-106° C.

Anal. Calcd. for C₁₂ H₁₃ N₃ O: C, 66.9; H, 6.1; N, 19.5. Found: C, 66.0;H, 6.0; N, 18.5.

EXAMPLE 23 1- and/or 2-Methyl-1H-3-(2-aminophenyl)pyrazole

A suspension of 30 g of the acetamide prepared in Example 22 in 75 ml ofconcentrated HCl was stirred and heated at reflux for 1 hour, thencooled to 10° C. and filtered. The solid isolated was added to about 300ml of ice-water, and the solution was made basic to a pH of about 8 byaddition of 50% NaOH to yield an oil. After extracting the aqueoussuspension with diethyl ether, the ether extract was concentrated invacuo to yield an oil that solidified on cooling. The solid wasrecrystallized from 1-chlorobutane to yield 20 g of the title compound;m.p. 82°-86° C.

Anal. Calcd. for C₁₀ H₁₁ N₃ : C, 69.3; H, 6.4; N, 24.2. Found: C, 69.0;H, 6.3; N, 23.9.

EXAMPLE 24 2-(1- and/or 2-Methyl-1H-pyrazol-3-yl)benzenesulfonamide

By the procedure of Example 4, 20 g of amine prepared in Example 23 wasdiazotized with 8.4 g of sodium nitrite and 42 ml of concentrated HCl in118 ml of glacial acetic acid. The diazonium salt suspension was addedto a suspension containing 4.9 g of cupric chloride dihydrate, 36 ml ofsulfur dioxide and 89 ml of acetic acid. After completion of reactionand addition of water, a precipitate formed. The mixture was filteredand the solid obtained was dissolved in methylene chloride and driedover sodium sulfate. Concentration of the methylene chloride solution invacuo yielded 27 g of crude 2-(1- and/or2-methyl-1H-pyrazol-3-yl)benzenesulfonyl chloride; m.p. 108°-115° C.

By the procedure of Example 5, 27 g of the above solid was reacted withabout 40 ml of concentrated NH₄ OH in 200 ml of tetrahydrofuran to yielda solid after work up. The solid was recrystallized from 2-propanol toyield 17 g of the title compound; m.p. 174°-177° C.

Anal. Calcd. for C₁₀ H₁₁ N₃ O₂ S: C, 50.6; H, 4.7; N, 17.7. Found: C,50.5; H, 4.6; N, 17.6.

EXAMPLE 25 N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(1-and/or2-methyl-1H-pyrazol-3-yl)benzenesulfonamide

By the procedure of Example 14, 2 g of the sulfonamide prepared inExample 24, was reacted with 0.7 g of trimethylaluminum (4.8 ml of 2Mtoluene solution) and 1.6 g ofmethyl(4,6-dimethoxypyrimidin-2-yl)carbamate in 100 ml of methylenechloride under a nitrogen atmosphere. After evaporation of the methylenechloride solvent in vacuo, the residue was recrystallized fromacetonitrile to yield 0.8 g of the title compound; m.p. 210°-212° C.

Anal. Calcd. for C₁₇ H₁₈ N₆ O₅ S: C, 48.8; H, 4.3; N, 20.1. Found: C,49.4; H, 4.5; N, 21.4.

EXAMPLE 26 2-(1H-Pyrazol-1-yl)benzenesulfonamide

A. To a solution of 52 g of 1-(2-bromophenyl)pyrazole in 230 ml ofdiethyl ether under a nitrogen atmosphere and cooled at -70° C. wasadded dropwise 175 ml of a 1.6M solution of n-butyl lithium in hexane.The suspension was allowed to warm from -70° C. to -25° C. on its own,then a solution of 37 ml of sulfuryl chloride in 69 ml of hexane wasadded dropwise at -25° C. to -20° C. After allowing the suspension towarm to room temperature, the suspension was stirred for 5 hours, thenfiltered to yield 38 g of crude 2-(1H-pyrazol-1-yl)benzenesulfonylchloride which was contaminated with inorganic salts.

B. To a suspension of the above solid in 200 ml of tetrahydrofurancooled at 10°-20° C. with an ice bath was added dropwise 50 ml ofconcentrated aqueous ammonium hydroxide. After adding 25 ml of water todissolve the salts present, the suspension was stirred at 25° C. for 10hours, then concentrated in vacuo. After adding water to the residue,the mixture was filtered and the residue was recrystallized from2-propanol to yield 11.2 g of the title compound; m.p. 167°-170° C.

Anal. Calcd. for C₉ H₉ N₃ O₂ S: C, 48.4; H, 4.1; N, 18.8. Found: C,48.1; H, 4.1; N, 18.9.

NMR (CDCl₃ -DMSO)δ: 6.5 (t, 1H, NC═CHC═N); 7.3 (br, 2H, SO₂ NH₂); and7.3-8.2 (m, 6H, arom-NCH═C--CHN).

EXAMPLE 27N-[(4-Methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-(1H-pyrazol-1-yl)benzenesulfonamide

By the procedure of Example 14, 1.3 g of the sulfonamide prepared inExample 26 was reacted in 100 ml of methylene chloride with 0.5 g oftrimethylaluminum (3.5 ml of 2M toluene solution) followed by 1.3 g ofmethyl (4-methoxy-6-methylpyrimidin-2-yl)carbamate. After work-up andevaporation of the methylene chloride solvent, the residue wastriturated with warm ethyl acetate to yield 1 g of the title compound;m.p. 200°-204° C.

Anal. Calcd. for C₁₆ H₁₆ N₆ O₄ S: C, 49.5; H, 4.2; N, 21.6. Found: C,48.8; H, 4.2; N, 21.3.

Using the techniques described in Equations 1 to 72 and Examples 1 to27, or simple modifications thereof, the following compounds in TablesI-VII can be made by one skilled in the art.

                                      TABLE I                                     __________________________________________________________________________     ##STR122##                                                                   R.sub.1                                                                            R.sub.2                                                                          R.sub.3                                                                           R.sub.13                                                                         X   Y        Z  W W" m.p. (°C.)                         __________________________________________________________________________    H    H  H   H  CH.sub.3                                                                          CH.sub.3 CH O O  180-185°                           H    H  H   H  CH.sub.3                                                                          OCH.sub.3                                                                              CH O O  185-189°                           H    H  H   H  CH.sub.3                                                                          CH.sub.3 N  O O  183-185°                           H    H  H   H  CH.sub.3                                                                          OCH.sub.3                                                                              N  O O  164- 172°                          H    H  H   H  OCH.sub.3                                                                         OCH.sub.3                                                                              N  O O  168-173°                           H    H  H   H  CH.sub.3                                                                          CH.sub.3 CH S O                                            H    H  H   H  OCH.sub.3                                                                         CH.sub.3 CH S O                                            H    H  H   H  OCH.sub.3                                                                         OCH.sub.3                                                                              CH S O                                            H    H  H   H  CH.sub.3                                                                          CH.sub.3 N  S O                                            H    H  H   H  OCH.sub.3                                                                         CH.sub.3 N  S O                                            H    H  H   H  OCH.sub.3                                                                         OCH.sub.3                                                                              N  S O                                            5-F  H  H   H  OCH.sub.3                                                                         OCH.sub.3                                                                              CH O O                                            6-Cl H  H   H  OCH.sub.3                                                                         OCH.sub.3                                                                              CH O O                                            4-Br H  H   H  OCH.sub.3                                                                         OCH.sub.3                                                                              CH O O                                            3-CH.sub.3                                                                         H  H   H  CH.sub.3                                                                          OCH.sub.3                                                                              N  O O                                            5-CF.sub.3                                                                         H  H   H  OCH.sub.3                                                                         OCH.sub.3                                                                              N  O O                                            5-OCH.sub.3                                                                        H  H   H  OCH.sub.3                                                                         OCH.sub.3                                                                              CH O O                                            H    H  H   CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                              CH O O                                            H    H  H   CH.sub.3                                                                         OCH.sub.3                                                                         CH.sub.3 N  O O                                            H    CH.sub.3                                                                         H   H  OCH.sub.3                                                                         OCH.sub.3                                                                              CH O O                                            H    CH.sub.3                                                                         H   H  CH.sub.3                                                                          OCH.sub.3                                                                              CH O O                                            H    CH.sub.3                                                                         H   H  CH.sub.3                                                                          CH.sub.3 CH O O                                            H    CH.sub.3                                                                         H   H  CH.sub.3                                                                          OCH.sub.3                                                                              N  O O                                            H    C.sub.2 H.sub.5                                                                  H   H  OCH.sub.3                                                                         OCH.sub.3                                                                              CH O O                                            H    C.sub.2 H.sub.5                                                                  H   H  CH.sub.3                                                                          OCH.sub.3                                                                              CH O O                                            H    C.sub.2 H.sub.5                                                                  H   H  CH.sub.3                                                                          CH.sub.3 CH O O                                            H    C.sub.2 H.sub.5                                                                  H   H  OCH.sub.3                                                                         CH.sub.3 N  O O                                            H    Cl H   H  OCH.sub.3                                                                         OCH.sub.3                                                                              CH O O                                            H    Br H   H  OCH.sub.3                                                                         OCH.sub.3                                                                              CH O O                                            H    H  CH.sub.3                                                                          H  OCH.sub.3                                                                         OCH.sub.3                                                                              CH O O                                            H    H  CH.sub.3                                                                          H  CH.sub.3                                                                          OCH.sub.3                                                                              CH O O                                            H    H  CH.sub.3                                                                          H  CH.sub.3                                                                          CH.sub.3 CH O O                                            H    H  CH.sub.3                                                                          H  OCH.sub.3                                                                         CH.sub.3 N  O O                                            H    H  C.sub.2 H.sub.5                                                                   H  OCH.sub.3                                                                         OCH.sub.3                                                                              CH O O                                            H    H  C.sub.2 H.sub.5                                                                   H  CH.sub.3                                                                          OCH.sub.3                                                                              CH O O                                            H    H  C.sub.2 H.sub.5                                                                   H  CH.sub.3                                                                          CH.sub.3 CH O O                                            H    H  C.sub.2 H.sub.5                                                                   H  CH.sub.3                                                                          OCH.sub.3                                                                              N  O O                                            H    H  Cl  H  OCH.sub.3                                                                         OCH.sub.3                                                                              CH S O                                            H    H  Br  H  OCH.sub.3                                                                         CH.sub.3 CH S O                                            H    H  OCH.sub.3                                                                         H  OCH.sub.3                                                                         OCH.sub.3                                                                              CH S O                                            H    H  OC.sub.2 H.sub.5                                                                  H  CH.sub.3                                                                          OCH.sub.3                                                                              CH S O                                            H    H  SCH.sub.3                                                                         H  CH.sub.3                                                                          CH.sub.3 CH S O                                            H    H  H   H  Cl  NH.sub.2 CH O O                                            H    H  H   H  Cl  OCH.sub.3                                                                              CH O O                                            H    H  H   H  Cl  NHCH.sub.3                                                                             CH O O                                            H    H  H   H  Cl  N(CH.sub.3).sub.2                                                                      CH O O                                            H    H  H   H  CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                     CH O O                                            H    H  H   H  CH.sub.3                                                                          C.sub.2 H.sub.5                                                                        CH O O                                            H    H  H   H  CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                       CH O O                                            H    H  H   H  OCH.sub.3                                                                         CH(OCH.sub.3).sub.2                                                                    CH O O                                            H    CH.sub.3                                                                         CH.sub.3                                                                          H  OCH.sub.3                                                                         OCH.sub.3                                                                              CH O O                                            H    CH.sub.3                                                                         CH.sub.3                                                                          H  OCH.sub.3                                                                         CH.sub.3 N  O O                                            H    CH.sub.3                                                                         CH.sub.3                                                                          H  OCH.sub.3                                                                         CH.sub.3 CH O O                                            H    H  CH.sub.3                                                                          H  OCH.sub.3                                                                         OCH.sub.3                                                                              N  O O                                            H    H  CH.sub.3                                                                          H  CH.sub.3                                                                          CH.sub.3 N  O O                                            H    CH.sub.3                                                                         H   H  OCH.sub.3                                                                         OCH.sub.3                                                                              N  O O                                            H    CH.sub.3                                                                         H   H  CH.sub.3                                                                          CH.sub.3 N  O O                                            H    CH.sub.3                                                                         CH.sub.3                                                                          H  CH.sub.3                                                                          CH.sub.3 CH O O                                            H    CH.sub.3                                                                         CH.sub.3                                                                          H  OCH.sub.3                                                                         OCH.sub.3                                                                              N  O O                                            H    CH.sub.3                                                                         CH.sub.3                                                                          H  CH.sub.3                                                                          CH.sub.3 N  O O                                            H    H  C.sub.2 H.sub.5                                                                   H  OCH.sub.3                                                                         OCH.sub.3                                                                              N  O O                                            H    H  C.sub.2 H.sub.5                                                                   H  CH.sub.3                                                                          CH.sub.3 N  O O                                            H    C.sub.2 H.sub.5                                                                  H   H  OCH.sub.3                                                                         OCH.sub.3                                                                              N  O O                                            H    C.sub.2 H.sub.5                                                                  H   H  CH.sub.3                                                                          CH.sub.3 N  O O                                            H    H  H   CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.3                                                                              CH O O                                            H    H  H   CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3 CH O O                                            H    H  H   CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                              N  O O                                            H    H  H   CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3 N  O O                                            H    H  H   H  OCH.sub.3                                                                         OCH.sub.3                                                                              CH O O  183-187°                           H    H  H   H  OCH.sub.3                                                                         OCH.sub.3                                                                              CH O S                                            H    H  H   H  OCH.sub.3                                                                         CH.sub.3 N  O S                                            H    H  H   H  CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                       CH O S                                            H    H  H   H  CH.sub.3                                                                          OCH.sub.2 CH.sub.2 OCH.sub.3                                                           N  O O                                            H    H  H   H  CH.sub.3                                                                          OCH.sub.2 CF.sub.3                                                                     N  O O                                            H    H  H   H  OCH.sub.3                                                                         SCH.sub.3                                                                              N  O O                                            H    H  H   H  CH.sub.3                                                                          CF.sub.3 CH O O                                            H    H  H   H  CH.sub.3                                                                           ##STR123##                                                                            CH O O                                            H    H  H   H  Cl  OC.sub.2 H.sub.5                                                                       CH O O                                            __________________________________________________________________________

                                      TABLE Ia                                    __________________________________________________________________________     ##STR124##                                                                   R       R.sub.1                                                                         R.sub.2                                                                          R.sub.3                                                                          R.sub.5                                                                          R.sub.13                                                                         X   Y      Z  W" m.p. (° C.)                     __________________________________________________________________________    CH.sub.3                                                                              H H  H  H  H  CH.sub.3                                                                          CH.sub.3                                                                             CH O  212-216°                        CH.sub.3                                                                              H H  H  H  H  CH.sub.3                                                                          OCH.sub.3                                                                            CH O  207-211°                        CH.sub.3                                                                              H H  H  H  H  OCH.sub.3                                                                         OCH.sub.3                                                                            N  O  190-195°                        CH.sub.3                                                                              H H  H  H  H  CH.sub.3                                                                          CH.sub.3                                                                             N  O  192-197°                        CH.sub.3                                                                              H H  H  H  H  CH.sub.3                                                                          OCH.sub.3                                                                            N  O  202-205°                        H       H H  H  H  H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O                                         C.sub.2 H.sub.5                                                                       H H  H  H  H  CH.sub.3                                                                          OCH.sub.3                                                                            CH O                                          -n-propyl                                                                            H H  H  H  H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O                                         CH(CH.sub.3).sub.2                                                                    H H  H  H  H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O                                         CH.sub.3                                                                              H H  H  H  CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                            CH O                                         CH.sub.3                                                                              H CH.sub.3                                                                         H  H  H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O                                         CH.sub.3                                                                              H CH.sub.3                                                                         H  H  H  OCH.sub.3                                                                         CH.sub.3                                                                             CH O                                         CH.sub.3                                                                              H CH.sub.3                                                                         H  H  H  OCH.sub.3                                                                         CH.sub.3                                                                             N  O                                         CH.sub.3                                                                              H H  CH.sub.3                                                                         CH.sub.3                                                                         H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O                                         CH.sub.3                                                                              H H  CH.sub.3                                                                         CH.sub.3                                                                         H  CH.sub.3                                                                          OCH.sub.3                                                                            CH O                                         CH.sub.3                                                                              H H  CH.sub.3                                                                         CH.sub.3                                                                         H  OCH.sub.3                                                                         CH.sub.3                                                                             N  O                                         CH.sub.3                                                                              H CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O                                         CH.sub.3                                                                              H CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H  OCH.sub.3                                                                         CH.sub.3                                                                             N  O                                         CH.sub.3                                                                              H C.sub.2 H.sub.5                                                                  H  H  H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O                                         CH.sub.3                                                                              H H  CH.sub.3                                                                         CH.sub.3                                                                         H  CH.sub.3                                                                          CH.sub.3                                                                             CH O                                         CH.sub.3                                                                              H H  CH.sub.3                                                                         CH.sub.3                                                                         H  OCH.sub.3                                                                         OCH.sub.3                                                                            N  O                                         CH.sub.3                                                                              H H  CH.sub.3                                                                         CH.sub.3                                                                         H  CH.sub.3                                                                          CH.sub.3                                                                             N  O                                         CH.sub.3                                                                              H CH.sub.3                                                                         H  H  H  CH.sub.3                                                                          CH.sub.3                                                                             CH O                                         CH.sub.3                                                                              H CH.sub.3                                                                         H  H  H  OCH.sub.3                                                                         OCH.sub.3                                                                            N  O                                         CH.sub.3                                                                              H CH.sub.3                                                                         H  H  H  CH.sub.3                                                                          CH.sub.3                                                                             N  O                                         CH.sub.3                                                                              H H  C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                  H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O                                         CH.sub.3                                                                              H H  C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                  H  OCH.sub.3                                                                         CH.sub.3                                                                             CH O                                         CH.sub.3                                                                              H H  C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                  H  OCH.sub.3                                                                         CH.sub.3                                                                             N  O                                         CH.sub.3                                                                              H H  C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                  H  CH.sub.3                                                                          CH.sub.3                                                                             CH O                                         CH.sub.3                                                                              H H  C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                  H  OCH.sub.3                                                                         OCH.sub.3                                                                            N  O                                         CH.sub.3                                                                              H H  H  H  H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O  210-212°                        CH.sub.3                                                                              H H  H  H  H  Cl  OCH.sub.3                                                                            CH O                                         CH.sub.2 (CH.sub.2).sub.2 CH.sub.3                                                    H H  H  H  H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O                                         CH.sub.3                                                                              H H  H  H  H  OCH.sub.3                                                                         CH(OCH.sub.3).sub.2                                                                  CH O                                         CH.sub.3                                                                              H H  H  H  H  OCH.sub.3                                                                         CH.sub.2 OCH.sub.3                                                                   CH O                                         CH.sub.3                                                                              H H  H  H  H  CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                     CH O                                         CH.sub.3                                                                              H H  H  H  H  OCH.sub.3                                                                          ##STR125##                                                                          CH O                                         CH.sub.3                                                                              H H  H  H  H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH S                                         __________________________________________________________________________

                                      TABLE Ib                                    __________________________________________________________________________     ##STR126##                                                                   R.sub.1                                                                         R.sub.2                                                                          R.sub.5                                                                           R.sub.13                                                                         X   Y      Z  W W" m.p. (°C.)                              __________________________________________________________________________    H H  H   H  CH.sub.3                                                                          OCH.sub.3                                                                            CH O O                                                 H H  H   H  CH.sub.3                                                                          CH.sub.3                                                                             CH O O                                                 H H  H   H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O O  189-193°                                H H  H   H  CH.sub.3                                                                          CH.sub.3                                                                             N  O O                                                 H H  H   H  OCH.sub.3                                                                         OCH.sub.3                                                                            N  O O                                                 H H  H   H  CH.sub.3                                                                          OCH.sub.3                                                                            N  O O                                                 H H  H   H  CH.sub.3                                                                          CH.sub.3                                                                             CH S O                                                 H H  H   H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH S O                                                 H H  H   H  OCH.sub.3                                                                         CH.sub.3                                                                             CH S O                                                 H H  H   H  CH.sub.3                                                                          CH.sub.3                                                                             N  S O                                                 H H  H   H  OCH.sub.3                                                                         OCH.sub.3                                                                            N  S O                                                 H H  H   H  CH.sub.3                                                                          OCH.sub.3                                                                            N  S O                                                 H H  H   CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                            CH O O                                                 H H  CH.sub.3                                                                          H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O O                                                 H H  CH.sub.3                                                                          H  OCH.sub.3                                                                         CH.sub.3                                                                             CH O O                                                 H H  CH.sub.3                                                                          H  CH.sub.3                                                                          CH.sub.3                                                                             CH O O                                                 H H  CH.sub.3                                                                          H  OCH.sub.3                                                                         CH.sub.3                                                                             N  O O                                                 H H  C.sub.2 H.sub.5                                                                   H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O O                                                 H H  C.sub.2 H.sub.5                                                                   H  OCH.sub.3                                                                         CH.sub.3                                                                             CH O O                                                 H H  C.sub.2 H.sub.5                                                                   H  CH.sub.3                                                                          CH.sub.3                                                                             CH O O                                                 H H  C.sub.2 H.sub.5                                                                   H  OCH.sub.3                                                                         CH.sub.3                                                                             N  O O                                                 H H  OCH.sub.3                                                                         H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O O                                                 H H  OCH.sub.3                                                                         H  CH.sub.3                                                                          OCH.sub.3                                                                            CH O O                                                 H H  OCH.sub.3                                                                         H  CH.sub.3                                                                          CH.sub.3                                                                             CH O O                                                 H H  OCH.sub.3                                                                         H  OCH.sub.3                                                                         CH.sub.3                                                                             N  O O                                                 H CH.sub.3                                                                         CH.sub.3                                                                          H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O O                                                 H CH.sub.3                                                                         CH.sub.3                                                                          H  OCH.sub.3                                                                         CH.sub.3                                                                             CH O O                                                 H H  Cl  H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH S O                                                 H H  Br  H  OCH.sub.3                                                                         CH.sub.3                                                                             CH S O                                                 H H  OCH.sub.3                                                                         H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH S O                                                 H H  OC.sub.2 H.sub.5                                                                  H  OCH.sub.3                                                                         CH.sub.3                                                                             CH S O                                                 H H  SCH.sub.3                                                                         H  CH.sub.3                                                                          CH.sub.3                                                                             CH S O                                                 H H  CH.sub.3                                                                          H  OCH.sub.3                                                                         OCH.sub.3                                                                            N  O O                                                 H H  CH.sub.3                                                                          H  CH.sub.3                                                                          CH.sub.3                                                                             N  O O                                                 H H  OCH.sub.3                                                                         H  OCH.sub.3                                                                         OCH.sub.3                                                                            N  O O                                                 H H  OCH.sub.3                                                                         H  CH.sub.3                                                                          CH.sub.3                                                                             N  O O                                                 H H  C.sub.2 H.sub.5                                                                   H  OCH.sub.3                                                                         OCH.sub.3                                                                            N  O O                                                 H H  H   H  Cl  OCH.sub.3                                                                            CH O O                                                 H H  H   H  OCH.sub.3                                                                         CH(OCH.sub.3).sub.2                                                                  CH O O                                                 H H  H   H  OCH.sub. 3                                                                        OCH.sub.3                                                                            CH O S                                                 __________________________________________________________________________

                                      TABLE Ic                                    __________________________________________________________________________     ##STR127##                                                                   R.sub.1                                                                         R.sub.12                                                                         R.sub.12 '                                                                       R.sub.13                                                                         X   Y      Z  W   W" m.p. (°C.)                             __________________________________________________________________________    H H  H  H  CH.sub.3                                                                          CH.sub.3                                                                             CH O   O  197-202°                               H H  H  H  OCH.sub.3                                                                         CH.sub.3                                                                             CH O   O  181-185°                               H H  H  H  CH.sub.3                                                                          CH.sub.3                                                                             N  O   O  187-192°                               H H  H  H  OCH.sub.3                                                                         OCH.sub.3                                                                            N  O   O  180-185°                               H H  H  H  CH.sub.3                                                                          OCH.sub.3                                                                            N  O   O  178-181°                               H CH.sub.3                                                                         H  H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O   O                                                H CH.sub.3                                                                         H  H  OCH.sub.3                                                                         CH.sub.3                                                                             CH O   O                                                H CH.sub.3                                                                         H  H  OCH.sub.3                                                                         CH.sub.3                                                                             N  O   O                                                H CH.sub.3                                                                         H  H  CH.sub.3                                                                          CH.sub.3                                                                             CH O   O                                                H CH.sub.3                                                                         CH.sub.3                                                                         H  CH.sub.3                                                                          CH.sub.3                                                                             CH O   O                                                H CH.sub.3                                                                         CH.sub.3                                                                         H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O   O                                                H CH.sub.3                                                                         CH.sub.3                                                                         H  OCH.sub.3                                                                         CH.sub.3                                                                             CH O   O                                                H CH.sub.3                                                                         CH.sub.3                                                                         H  OCH.sub.3                                                                         CH.sub.3                                                                             N  O   O                                                H H  H  CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                            CH O   O                                                H H  H  CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.3                                                                            CH O   O                                                H H  H  H  CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                   CH O   O                                                H H  H  H  CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                     CH O   O                                                H H  H  H  OCH.sub.3                                                                         CH(OCH.sub.3).sub.2                                                                  CH O   O                                                H H  H  H  CH.sub.3                                                                          C.sub.2 H.sub.5                                                                      CH O   O                                                H H  H  H  Cl  OCH.sub.3                                                                            CH O   O                                                H H  H  H  Cl  NH.sub.2                                                                             CH O   O                                                H H  H  H  Cl  NHCH.sub.3                                                                           CH O   O                                                H H  H  H  Cl  N(CH.sub.3).sub.2                                                                    CH O   O                                                H H  H  H  CH.sub.3                                                                          CH.sub.3                                                                             CH NCH.sub.3                                                                         O  218-222°                               H H  H  H  OCH.sub.3                                                                         CH.sub.3                                                                             CH NCH.sub.3                                                                         O  222-226°                               H H  H  H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH NCH.sub.3                                                                         O  220-226°                               H H  H  H  CH.sub.3                                                                          CH.sub.3                                                                             N  NCH.sub.3                                                                         O  232-237°                               H H  H  H  OCH.sub.3                                                                         OCH.sub.3                                                                            N  NCH.sub.3                                                                         O  195-200°                               H CH.sub.3                                                                         H  H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH NCH.sub.3                                                                         O                                                H CH.sub.3                                                                         H  H  OCH.sub.3                                                                         CH.sub.3                                                                             CH NCH.sub.3                                                                         O                                                H CH.sub.3                                                                         H  H  CH.sub.3                                                                          CH.sub.3                                                                             CH NCH.sub.3                                                                         O                                                H CH.sub.3                                                                         H  H  OCH.sub.3                                                                         CH.sub.3                                                                             N  NCH.sub.3                                                                         O                                                H CH.sub.3                                                                         CH.sub.3                                                                         H  CH.sub.3                                                                          CH.sub.3                                                                             CH NCH.sub.3                                                                         O                                                H CH.sub.3                                                                         CH.sub.3                                                                         H  OCH.sub.3                                                                         CH.sub.3                                                                             CH NCH.sub.3                                                                         O                                                H CH.sub.3                                                                         CH.sub.3                                                                         H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH NCH.sub.3                                                                         O                                                H CH.sub.3                                                                         CH.sub.3                                                                         H  CH.sub.3                                                                          OCH.sub.3                                                                            N  NCH.sub.3                                                                         O                                                H CH.sub.3                                                                         CH.sub.3                                                                         H  OCH.sub.3                                                                         OCH.sub.3                                                                            N  NCH.sub.3                                                                         O                                                H H  H  H  CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                   CH NCH.sub.3                                                                         O                                                H H  H  H  CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                     CH NCH.sub.3                                                                         O                                                H H  H  H  CH.sub.3                                                                          CH(OCH.sub.3).sub.2                                                                  CH NCH.sub.3                                                                         O                                                H H  H  CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                            CH NCH.sub.3                                                                         O                                                H H  H  CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.3                                                                            CH NCH.sub.3                                                                         O                                                H H  H  H  CH.sub.3                                                                          CH.sub.3                                                                             CH S   O                                                H H  H  H  OCH.sub.3                                                                         CH.sub.3                                                                             CH S   O                                                H H  H  H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH S   O                                                H H  H  H  CH.sub.3                                                                          CH.sub.3                                                                             N  S   O                                                H H  H  H  CH.sub.3                                                                          OCH.sub.3                                                                            N  S   O                                                H H  H  H  OCH.sub.3                                                                         OCH.sub.3                                                                            N  S   O                                                H CH.sub.3                                                                         H  H  OCH.sub.3                                                                         OCH.sub.3                                                                            N  O   O                                                H CH.sub.3                                                                         H  H  CH.sub.3                                                                          CH.sub.3                                                                             N  O   O                                                H CH.sub.3                                                                         CH.sub.3                                                                         H  OCH.sub.3                                                                         OCH.sub.3                                                                            N  O   O                                                H CH.sub.3                                                                         CH.sub.3                                                                         H  CH.sub.3                                                                          CH.sub.3                                                                             N  O   O                                                H H  H  H  OCH.sub. 3                                                                        OCH.sub.3                                                                            CH O   O  175-178°                               H H  H  H  OCH.sub.3                                                                         CH.sub.3                                                                             N  NCH.sub.3                                                                         O  221-224°                               __________________________________________________________________________

                                      TABLE Id                                    __________________________________________________________________________     ##STR128##                                                                   R.sub.1                                                                         R.sub.4 R.sub.6                                                                          R.sub.7 R.sub.13                                                                         X   Y      Z  W" m.p. (°C.)                    __________________________________________________________________________    H H       H  H       H  CH.sub.3                                                                          CH.sub.3                                                                             CH O  198-202°                      H H       H  H       H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O  194-198°                      H H       H  H       H  OCH.sub.3                                                                         CH.sub.3                                                                             CH O  200-204°                      H H       H  H       H  OCH.sub.3                                                                         OCH.sub.3                                                                            N  O  188-192°                      H H       H  H       H  OCH.sub.3                                                                         CH.sub.3                                                                             N  O  184-188°                      H CH.sub.3                                                                              H  CH.sub.3                                                                              H  CH.sub.3                                                                          CH.sub.3                                                                             CH O                                       H CH.sub.3                                                                              H  CH.sub.3                                                                              H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O                                       H CH.sub.3                                                                              H  CH.sub.3                                                                              H  OCH.sub.3                                                                         CH.sub.3                                                                             CH O                                       H CH.sub.3                                                                              H  CH.sub.3                                                                              H  OCH.sub.3                                                                         OCH.sub.3                                                                            N  O                                       H CH.sub.3                                                                              H  CH.sub.3                                                                              H  OCH.sub.3                                                                         CH.sub.3                                                                             N  O                                       H CH.sub.3                                                                              H  CH.sub.3                                                                              H  CH.sub.3                                                                          CH.sub.3                                                                             N  O                                       H H       H  H       CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                            CH O                                       H CH.sub.3                                                                              C.sub.2 H.sub.5                                                                  CH.sub.3                                                                              H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O                                       H H       C.sub.2 H.sub.5                                                                  H       H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O                                       H CH.sub.3                                                                              CH.sub.3                                                                         CH.sub.3                                                                              H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O                                       H CH.sub.3                                                                              CH.sub.3                                                                         CH.sub.3                                                                              H  OCH.sub.3                                                                         CH.sub.3                                                                             CH O                                       H CH.sub.3                                                                              CH.sub.3                                                                         CH.sub.3                                                                              H  OCH.sub.3                                                                         CH.sub.3                                                                             N  O                                       H CH.sub.2 CH.sub.2 CH.sub.3                                                            H  H       H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O                                       H H       H  CH(CH.sub.3).sub.2                                                                    H  OCH.sub.3                                                                         CH.sub.3                                                                             N  O                                       H H       H  H       H  CH.sub.3                                                                          CH.sub.3                                                                             N  O  201-205°                      H C.sub.2 H.sub.5                                                                       H  C.sub.2 H.sub.5                                                                       H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O                                       H CH.sub.2 (CH.sub.2).sub.2 CH.sub.3                                                    H  H       H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O                                       H H       H  CH.sub.2 (CH.sub.2).sub.2 CH.sub.3                                                    H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH O                                       H H       H  H       H  Cl  OCH.sub.3                                                                            CH O                                       H H       H  H       H  OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                      CH O                                       H H       H  H       H  CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                     CH H                                       H H       H  H       H  OCH.sub.3                                                                         CH.sub.2 OCH.sub.3                                                                   CH O                                       H H       H  H       H  OCH.sub.3                                                                         CH(OCH.sub.3).sub.2                                                                  CH O                                       H H       H  H       H  CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                     N  O                                       H H       H  H       H  OCH.sub.3                                                                         OCH.sub.3                                                                            CH S                                       H H       H  H       H  OCH.sub.3                                                                         SCH.sub.3                                                                            CH O                                       H H       H  H       H  CH.sub.3                                                                          CF.sub.3                                                                             CH O                                       __________________________________________________________________________

                  TABLE II                                                        ______________________________________                                         ##STR129##                                                                                                         m.p.                                    R.sub.1R.sub.5                                                                         R.sub.13                                                                             X       Y        Z    W'W"(°C.)                        ______________________________________                                        HH       H      CH.sub.3                                                                              CH.sub.3 CH   O   O                                   HH       H      OCH.sub.3                                                                             OCH.sub.3                                                                              CH   O   O                                   HH       H      OCH.sub.3                                                                             CH.sub.3 CH   O   O                                   HH       H      CH.sub.3                                                                              CH.sub.3 N    O   O                                   HH       H      OCH.sub.3                                                                             OCH.sub.3                                                                              N    O   O                                   HH       H      OCH.sub.3                                                                             CH.sub.3 N    O   O                                   HCH.sub.3                                                                              H      CH.sub.3                                                                              CH.sub.3 CH   O   O   209-                                                                          212°                     HCH.sub.3                                                                              H      OCH.sub.3                                                                             OCH.sub.3                                                                              CH   O   O   214-                                                                          218°                     HCH.sub.3                                                                              H      CH.sub.3                                                                              OCH.sub.3                                                                              CH   O   O   196-                                                                          200°                     HCH.sub.3                                                                              H      CH.sub.3                                                                              CH.sub.3 N    O   O   182-                                                                          192°                     HCH.sub.3                                                                              H      OCH.sub.3                                                                             OCH.sub.3                                                                              N    O   O                                   HCH.sub.3                                                                              H      OCH.sub.3                                                                             CH.sub.3 N    O   O   186-                                                                          190°                     HC.sub.2 H.sub.5                                                                       H      CH.sub.3                                                                              CH.sub.3 CH   O   O                                   HC.sub.2 H.sub.5                                                                       H      OCH.sub.3                                                                             OCH.sub.3                                                                              CH   O   O                                   HC.sub.2 H.sub.5                                                                       H      CH.sub.3                                                                              OCH.sub.3                                                                              CH   O   O                                   HC.sub.2 H.sub.5                                                                       H      CH.sub.3                                                                              CH.sub.3 N    O   O                                   HC.sub. 2 H.sub.5                                                                      H      OCH.sub.3                                                                             OCH.sub.3                                                                              N    O   O                                   HC.sub.2 H.sub.5                                                                       H      CH.sub.3                                                                              OCH.sub.3                                                                              N    O   O                                   HCH.sub.3                                                                              H      Cl      NH.sub.2 CH   O   O                                   HH       H      CH.sub.3                                                                              CH.sub.3 CH   S   O                                   HH       H      OCH.sub.3                                                                             OCH.sub.3                                                                              CH   S   O                                   HH       H      OCH.sub.3                                                                             CH.sub.3 CH   S   O                                   HH       H      CH.sub.3                                                                              CH.sub.3 N    S   O                                   HH       H      OCH.sub.3                                                                             OCH.sub.3                                                                              N    S   O                                   HH       H      OCH.sub.3                                                                             CH.sub.3 N    S   O                                   HCH.sub.3                                                                              H      CH.sub.3                                                                              CH.sub.3 CH   S   O                                   HCH.sub.3                                                                              H      OCH.sub.3                                                                             OCH.sub.3                                                                              CH   S   O   227-                                                                          230°                     HCH.sub.3                                                                              H      OCH.sub.3                                                                             CH.sub.3 CH   S   O                                   HCH.sub.3                                                                              H      CH.sub.3                                                                              CH.sub.3 N    S   O                                   HCH.sub.3                                                                              H      OCH.sub.3                                                                             OCH.sub.3                                                                              N    S   O                                   HCH.sub.3                                                                              H      CH.sub.3                                                                              OCH.sub.3                                                                              N    S   O                                    HC.sub.2 H.sub.5                                                                      H      OCH.sub.3                                                                             OCH.sub.3                                                                              CH   S   O                                   HC.sub.2 H.sub.5                                                                       H      OCH.sub.3                                                                             CH.sub.3 CH   S   O                                   HC.sub.2 H.sub.5                                                                       H      CH.sub.3                                                                              OCH.sub.3                                                                              N    S   O                                   HH       CH.sub.3                                                                             OCH.sub.3                                                                             OCH.sub.3                                                                              CH   O   O                                   5-FCH.sub.3                                                                            H      OCH.sub.3                                                                             OCH.sub.3                                                                              CH   O   O                                   6-ClCH.sub.3                                                                           H      OCH.sub.3                                                                             OCH.sub.3                                                                              CH   O   O                                   4-BrCH.sub.3                                                                           H      OCH.sub.3                                                                             CH.sub.3 CH   O   O                                   3-CH.sub.3CH.sub.3                                                                     H      OCH.sub.3                                                                             OCH.sub.3                                                                              CH   O   O                                   5-CF.sub.3CH.sub.3                                                                     H      OCH.sub.3                                                                             OCH.sub.3                                                                              CH   O   O                                   5-OCH.sub.3CH.sub.3                                                                    H      OCH.sub.3                                                                             OCH.sub.3                                                                              CH   O   O                                   HCH.sub.3                                                                              H      Cl      OCH.sub.3                                                                              CH   O   O                                   HCH.sub.3                                                                              H      Cl      NHCH.sub.3                                                                             CH   O   O                                   HCH.sub.3                                                                              H      Cl      N(CH.sub.3).sub.2                                                                      CH   O   O                                   HCH.sub.3                                                                              H      CH.sub.3                                                                              CH.sub.2 OCH.sub.3                                                                     CH   O   O                                   HCH.sub.3                                                                              H      CH.sub.3                                                                              C.sub. 2 H.sub.5                                                                       CH   O   O                                   HCH.sub.3                                                                              H      CH.sub.3                                                                              OC.sub.2 H.sub.5                                                                       CH   O   O                                   HCH.sub.3                                                                              H      OCH.sub.3                                                                             CH(OCH.sub.3).sub.2                                                                    CH   O   O                                   HC.sub.2 H.sub.5                                                                       H      CH.sub.3                                                                              CH.sub.3 CH   S   O                                   HC.sub.2 H.sub.5                                                                       H      OCH.sub.3                                                                             OCH.sub.3                                                                              N    S   O                                   HC.sub.2 H.sub.5                                                                       H      CH.sub.3                                                                              CH.sub.3 N    S   O                                   HCH.sub.3                                                                              H      OCH.sub.3                                                                             OCH.sub.3                                                                              CH   O   S                                   HCH.sub.3                                                                              H      OCH.sub.3                                                                             CH.sub.3 N    O   S                                   HCH.sub.3                                                                              H      OCH.sub.3                                                                              ##STR130##                                                                            CH   O   O                                   ______________________________________                                    

                  TABLE IIa                                                       ______________________________________                                         ##STR131##                                                                   R.sub.1                                                                           R.sub.5 R.sub.13                                                                             X     Y     Z    W'  W"   m.p. (°C.)                ______________________________________                                        H   H       H      CH.sub.3                                                                            CH.sub.3                                                                            CH   O   O                                     H   H       H      OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O   O                                     H   H       H      CH.sub.3                                                                            OCH.sub.3                                                                           CH   O   O                                     H   H       H      CH.sub.3                                                                            CH.sub.3                                                                            N    O   O                                     H   H       H      OCH.sub.3                                                                           OCH.sub.3                                                                           N    O   O                                     H   H       H      CH.sub.3                                                                            OCH.sub.3                                                                           N    O   O                                     H   CH.sub.3                                                                              H      CH.sub.3                                                                            CH.sub.3                                                                            CH   O   O                                     H   CH.sub. 3                                                                             H      OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O   O                                     H   CH.sub.3                                                                              H      CH.sub.3                                                                            OCH.sub.3                                                                           CH   O   O                                     H   CH.sub.3                                                                              H      CH.sub.3                                                                            CH.sub.3                                                                            N    O   O                                     H   CH.sub.3                                                                              H      OCH.sub.3                                                                           OCH.sub.3                                                                           N    O   O                                     H   CH.sub.3                                                                              H      CH.sub.3                                                                            OCH.sub.3                                                                           N    O   O                                     H   C.sub.2 H.sub.5                                                                       H      CH.sub.3                                                                            CH.sub.3                                                                            CH   O   O                                     H   C.sub.2 H.sub.5                                                                       H      OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O   O                                     H   C.sub.2 H.sub.5                                                                       H      CH.sub.3                                                                            OCH.sub.3                                                                           CH   O   O                                     H   C.sub.2 H.sub.5                                                                       H      CH.sub.3                                                                            OCH.sub.3                                                                           N    O   O                                     H   C.sub.2 H.sub.5                                                                       H      OCH.sub.3                                                                           OCH.sub.3                                                                           N    O   O                                     H   SCH.sub.3                                                                             H      OCH.sub.3                                                                           OCH.sub.3                                                                           CH   S   O                                     H   OCH.sub.3                                                                             H      OCH.sub.3                                                                           OCH.sub.3                                                                           CH   S   O                                     H   OC.sub.2 H.sub.5                                                                      H      OCH.sub.3                                                                           OCH.sub.3                                                                           CH   S   O                                     H   Cl      H      OCH.sub.3                                                                           OCH.sub.3                                                                           CH   S   O                                     H   Br      H      OCH.sub.3                                                                           CH.sub.3                                                                            CH   S   O                                     H   H       CH.sub.3                                                                             OCH.sub.3                                                                           CH.sub.3                                                                            CH   O   O                                     H   C.sub.2 H.sub.5                                                                       H      CH.sub.3                                                                            CH.sub.3                                                                            N    O   O                                     H   H       H      CH.sub.3                                                                            CH.sub.3                                                                            CH   S   O                                     H   H       H      OCH.sub.3                                                                           OCH.sub.3                                                                           CH   S   O                                     H   H       H      CH.sub.3                                                                            OCH.sub.3                                                                           CH   S   O                                     H   H       H      CH.sub.3                                                                            CH.sub.3                                                                            N    S   O                                     H   H       H      OCH.sub.3                                                                           OCH.sub.3                                                                           N    S   O                                     H   H       H      CH.sub.3                                                                            OCH.sub.3                                                                           N    S   O                                     H   Cl      H      CH.sub.3                                                                            CH.sub.3                                                                            CH   S   O                                     H   Cl      H      CH.sub.3                                                                            OCH.sub.3                                                                           CH   S   O                                     H   Cl      H      CH.sub.3                                                                            CH.sub.3                                                                            N    S   O                                     H   Cl      H      OCH.sub.3                                                                           OCH.sub.3                                                                           N    S   O                                     H   Cl      H      CH.sub.3                                                                            OCH.sub.3                                                                           N    S   O                                     ______________________________________                                    

                  TABLE IIb                                                       ______________________________________                                         ##STR132##                                                                                                           m.p.                                  R.sub.1                                                                           R.sub.5                                                                              R.sub.13                                                                             X     Y          Z    W'W"(°C.)                      ______________________________________                                        H   H      H      CH.sub.3                                                                            CH.sub.3   CH   O   O                                 H   H      H      OCH.sub.3                                                                           OCH.sub.3  CH   O   O                                 H   H      H      CH.sub.3                                                                            OCH.sub.3  CH   O   O                                 H   H      H      CH.sub.3                                                                            CH.sub.3   N    O   O                                 H   H      H      OCH.sub.3                                                                           OCH.sub.3  N    O   O                                 H   H      H      OCH.sub.3                                                                           CH.sub.3   N    O   O                                 H   CH.sub.3                                                                             H      CH.sub.3                                                                            CH.sub.3   CH   O   O   202-                                                                          206°                   H   CH.sub.3                                                                             H      OCH.sub.3                                                                           OCH.sub.3  CH   O   O   230-                                                                          234°                   H   CH.sub.3                                                                             H      CH.sub.3                                                                            OCH.sub.3  CH   O   O   189-                                                                          193°                   H   CH.sub.3                                                                             H      CH.sub.3                                                                            CH.sub.3   N    O   O   211-                                                                          214°                   H   CH.sub.3                                                                             H      OCH.sub.3                                                                           OCH.sub.3  N    O   O   194-                                                                          198°                   H   CH.sub.3                                                                             H      CH.sub.3                                                                            OCH.sub.3  N    O   O   188-                                                                          192°                   H   H      H      CH.sub.3                                                                            CH.sub.3   CH   S   O                                 H   H      H      OCH.sub.3                                                                           OCH.sub.3  CH   S   O                                 H   H      H      CH.sub.3                                                                            OCH.sub.3  CH   S   O                                 H   H      H      CH.sub.3                                                                            CH.sub.3   N    S   O                                 H   H      H      OCH.sub.3                                                                           OCH.sub.3  N    S   O                                 H   H      H      OCH.sub.3                                                                           CH.sub.3   N    S   O                                 H   H      CH.sub.3                                                                             OCH.sub. 3                                                                          OCH.sub.3  CH   O   O                                 H   C.sub.2 H.sub.5                                                                      H      OCH.sub.3                                                                           OCH.sub.3  CH   O   O                                 H   C.sub.2 H.sub.5                                                                      H      OCH.sub.3                                                                           CH.sub.3   CH   O   O                                 H   C.sub.2 H.sub.5                                                                      H      OCH.sub.3                                                                           CH.sub.3   N    O   O                                 H   CH.sub.3                                                                             H      OCH.sub.3                                                                           OCH.sub.3  CH   S   O                                 H   CH.sub.3                                                                             H      OCH.sub.3                                                                           CH.sub.3   CH   S   O                                 H   CH.sub.3                                                                             H      OCH.sub.3                                                                           CH.sub.3   N    S   O                                 H   CH.sub.3                                                                             H      OCH.sub.3                                                                           OCH.sub.3  CH   O   S                                 H   CH.sub.3                                                                             H      CH.sub.3                                                                            OCH.sub.2 CH.sub.2 OCH.sub.3                                                             N    O   O                                 H   CH.sub.3                                                                             H      CH.sub.3                                                                            OCH.sub.2 CF.sub.3                                                                       N    O   O                                 H   CH.sub.3                                                                             H      OCH.sub.3                                                                           SCH.sub.3  N    O   O                                 H   CH.sub.3                                                                             H      CH.sub.3                                                                            CF.sub.3   CH   O   O                                 H   CH.sub.3                                                                             H      OCH.sub.3                                                                            ##STR133##                                                                              CH   O   O                                 H   CH.sub.3                                                                             H      OCH.sub.3                                                                           CH.sub.2 OCH.sub.3                                                                       CH   O   O                                 H   CH.sub.3                                                                             H      CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                         N    O   O                                 H   CH.sub.3                                                                             H      OCH.sub.3                                                                           CH(OCH.sub.3).sub.2                                                                      CH   O   O                                 ______________________________________                                    

                  TABLE IIc                                                       ______________________________________                                         ##STR134##                                                                   R.sub.1                                                                           R.sub.13                                                                             R.sub.14                                                                              X     Y     Z    W'  W"   m.p. (°C.)                ______________________________________                                        H   H      H       CH.sub.3                                                                            CH.sub.3                                                                            CH   O   O                                     H   H      H       OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O   O                                     H   H      H       CH.sub.3                                                                            OCH.sub.3                                                                           CH   O   O                                     H   H      H       CH.sub.3                                                                            CH.sub.3                                                                            N    O   O                                     H   H      H       OCH.sub.3                                                                           OCH.sub.3                                                                           N    O   O                                     H   H      H       OCH.sub.3                                                                           CH.sub.3                                                                            N    O   O                                     H   H      Cl      OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O   O                                     H   H      Cl      CH.sub.3                                                                            OCH.sub.3                                                                           CH   O   O                                     H   H      OCH.sub.3                                                                             CH.sub.3                                                                            CH.sub.3                                                                            CH   S   O                                     H   H      Cl      OCH.sub.3                                                                           OCH.sub.3                                                                           N    O   O                                     H   H      Cl      CH.sub.3                                                                            OCH.sub.3                                                                           N    O   O                                     H   H      OCH.sub.3                                                                             OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O   O                                     H   H      OC.sub.2 H.sub.5                                                                      OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O   O                                     H   H      SCH.sub.3                                                                             OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O   O                                     H   CH.sub.3                                                                             H       OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O   O                                     H   H      H       CH.sub.3                                                                            CH.sub.3                                                                            CH   S   O                                     H   H      H       CH.sub.3                                                                            OCH.sub.3                                                                           CH   S   O                                     H   H      H       OCH.sub.3                                                                           OCH.sub.3                                                                           CH   S   O                                     H   H      H       CH.sub.3                                                                            CH.sub.3                                                                            N    S   O                                     H   H      H       CH.sub.3                                                                            OCH.sub.3                                                                           N    S   O                                     H   H      H       OCH.sub.3                                                                           OCH.sub.3                                                                           N    S   O                                     H   H      Cl      OCH.sub.3                                                                           OCH.sub.3                                                                           CH   S   O                                     H   H      Cl      OCH.sub.3                                                                           CH.sub.3                                                                            CH   S   O                                     H   H      Cl      OCH.sub.3                                                                           CH.sub.3                                                                            N    S   O                                     H   H      OC.sub.2 H.sub.5                                                                      OCH.sub.3                                                                           OCH.sub.3                                                                           CH   S   O                                     H   H      SCH.sub.3                                                                             OCH.sub.3                                                                           OCH.sub.3                                                                           CH   S   O                                     H   H      CH.sub.3                                                                              OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O   O                                     H   H      C.sub.2 H.sub.5                                                                       OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O   O                                     ______________________________________                                    

                  TABLE IId                                                       ______________________________________                                         ##STR135##                                                                   R.sub.1                                                                           R.sub.6                                                                              R.sub.13                                                                             X     Y        Z    W"   m.p. (°C.)                  ______________________________________                                        H   H      H      CH.sub.3                                                                            CH.sub.3 CH   O    189-192°                    H   H      H      CH.sub.3                                                                            OCH.sub.3                                                                              CH   O    190-193°                    H   H      H      OCH.sub.3                                                                           OCH.sub.3                                                                              CH   O    199-203°                    H   H      H      CH.sub.3                                                                            CH.sub.3 N    O    190-194°                    H   H      H      OCH.sub.3                                                                           CH.sub.3 N    O    174-177°                    H   H      H      OCH.sub.3                                                                           OCH.sub.3                                                                              N    O    167-172°                    H   CH.sub.3                                                                             H      OCH.sub.3                                                                           OCH.sub.3                                                                              CH   O                                       H   CH.sub. 3                                                                            H      CH.sub.3                                                                            OCH.sub.3                                                                              N    O                                       H   C.sub.2 H.sub.5                                                                      H      OCH.sub.3                                                                           OCH.sub.3                                                                              CH   O                                       H   C.sub.2 H.sub.5                                                                      H      CH.sub.3                                                                            OCH.sub.3                                                                              N    O                                       H   H      CH.sub.3                                                                             OCH.sub.3                                                                           OCH.sub.3                                                                              CH   O                                       H   H      H      OCH.sub.3                                                                           OCH.sub.3                                                                              CH   S                                       H   H      H      Cl    OCH.sub.3                                                                              CH   O                                       H   H      H      OCH.sub.3                                                                           CH.sub.2 OCH.sub.3                                                                     CH   O                                       H   H      H      CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                       N    O                                       H   H      H      OCH.sub.3                                                                           CH(OCH.sub.3).sub.2                                                                    CH   O                                       H   H      H      OCH.sub.3                                                                            ##STR136##                                                                            CH   O                                       H   H      H      OCH.sub.3                                                                           SCH.sub.3                                                                              N    O                                       H   H      H      CH.sub.3                                                                            CF.sub.3 CH   O                                       H   H      H      OCH.sub.3                                                                           C.sub.2 H.sub.5                                                                        CH   O                                       H   H      H      Cl    NH.sub.2 CH   O                                       ______________________________________                                    

                  TABLE IIe                                                       ______________________________________                                         ##STR137##                                                                   R.sub.1                                                                           R.sub.6                                                                              R.sub.13                                                                             X     Y        Z    W"   m.p. (°C.)                  ______________________________________                                        H   H      H      CH.sub.3                                                                            CH.sub.3 CH   O                                       H   H      H      CH.sub.3                                                                            OCH.sub.3                                                                              CH   O                                       H   H      H      OCH.sub.3                                                                           OCH.sub.3                                                                              CH   O                                       H   H      H      CH.sub.3                                                                            CH.sub.3 N    O                                       H   H      H      OCH.sub.3                                                                           CH.sub.3 N    O                                       H   H      H      OCH.sub.3                                                                           OCH.sub.3                                                                              N    O                                       H   CH.sub.3                                                                             H      OCH.sub.3                                                                           OCH.sub.3                                                                              CH   O                                       H   CH.sub.3                                                                             H      CH.sub.3                                                                            OCH.sub.3                                                                              N    O                                       H   C.sub.2 H.sub.5                                                                      H      OCH.sub.3                                                                           OCH.sub.3                                                                              CH   O                                       H   C.sub.2 H.sub.5                                                                      H      CH.sub.3                                                                            OCH.sub.3                                                                              N    O                                       H   H      CH.sub.3                                                                             OCH.sub.3                                                                           OCH.sub.3                                                                              CH   O                                       H   H      H      OCH.sub.3                                                                           OCH.sub.3                                                                              CH   S                                       H   H      H      Cl    OCH.sub.3                                                                              CH   O                                       H   H      H      OCH.sub.3                                                                           CH.sub.2 OCH.sub.3                                                                     CH   O                                       H   H      H      CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                       N    O                                       H   H      H      OCH.sub.3                                                                           CH(OCH.sub.3).sub.2                                                                    CH   O                                       H   H      H      OCH.sub.3                                                                            ##STR138##                                                                            CH   O                                       H   H      H      OCH.sub.3                                                                           SCH.sub.3                                                                              N    O                                       H   H      H      CH.sub.3                                                                            CF.sub.3 CH   O                                       H   H      H      OCH.sub.3                                                                           C.sub.2 H.sub.5                                                                        CH   O                                       H   H      H      Cl    NH.sub.2 CH   O                                       ______________________________________                                    

                                      TABLE III                                   __________________________________________________________________________     ##STR139##                                                                   R.sub.1                                                                         R.sub.4 R.sub.13                                                                         R.sub.15                                                                             X   Y   Z  W" m.p. (°C.)                           __________________________________________________________________________    H CH.sub.3                                                                              H  CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                          CH O                                              H CH.sub.3                                                                              H  CH.sub.3                                                                             OCH.sub.3                                                                         OCH.sub.3                                                                         CH O                                              H CH.sub.3                                                                              H  CH.sub.3                                                                             CH.sub.3                                                                          OCH.sub.3                                                                         CH O                                              H CH.sub.3                                                                              H  CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                          N  O                                              H CH.sub.3                                                                              H  CH.sub.3                                                                             OCH.sub.3                                                                         OCH.sub.3                                                                         N  O                                              H CH.sub.3                                                                              H  CH.sub.3                                                                             CH.sub.3                                                                          OCH.sub.3                                                                         N  O                                              H H       H  CH.sub.3                                                                             OCH.sub.3                                                                         OCH.sub.3                                                                         CH O                                              H C.sub.2 H.sub.5                                                                       H  CH.sub.3                                                                             OCH.sub.3                                                                         OCH.sub.3                                                                         CH O                                              H C.sub.2 H.sub.5                                                                       H  CH.sub.3                                                                             OCH.sub.3                                                                         CH.sub.3                                                                          N  O                                              H CH.sub.2 CH.sub.2 CH.sub.3                                                            H  CH.sub.3                                                                             OCH.sub.3                                                                         OCH.sub.3                                                                         CH O                                              H CH.sub.2 (CH.sub.2).sub.2 CH.sub.3                                                    H  CH.sub.3                                                                             OCH.sub.3                                                                         CH.sub.3                                                                          N  O                                              H CH.sub.3                                                                              H  C.sub.2 H.sub.5                                                                      OCH.sub.3                                                                         OCH.sub.3                                                                         CH O                                              H CH.sub.3                                                                              H  CH.sub.2 CH.sub.2 CH.sub.3                                                           OCH.sub.3                                                                         OCH.sub.3                                                                         CH O                                              H CH.sub.3                                                                              H  CH(CH.sub.3).sub.2                                                                   OCH.sub.3                                                                         OCH.sub.3                                                                         CH O                                              H CH.sub.3                                                                              CH.sub.3                                                                         CH.sub.3                                                                             OCH.sub.3                                                                         OCH.sub.3                                                                         CH O                                              __________________________________________________________________________

                  TABLE IIIa                                                      ______________________________________                                         ##STR140##                                                                   R.sub.1                                                                              R.sub.6                                                                              R.sub.13                                                                             X     Y     Z    W"   m.p. (°C.)                  ______________________________________                                        H      H      H      CH.sub.3                                                                            CH.sub.3                                                                            CH   O                                       H      H      H      CH.sub.3                                                                            OCH.sub.3                                                                           CH   O                                       H      H      H      OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O                                       H      H      H      CH.sub.3                                                                            CH.sub.3                                                                            N    O                                       H      H      H      CH.sub.3                                                                            OCH.sub.3                                                                           N    O                                       H      H      H      OCH.sub.3                                                                           OCH.sub.3                                                                           N    O                                       H      CH.sub.3                                                                             H      CH.sub.3                                                                            CH.sub.3                                                                            CH   O                                       H      CH.sub.3                                                                             H      OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O                                       H      CH.sub.3                                                                             H      CH.sub.3                                                                            OCH.sub.3                                                                           CH   O                                       H      CH.sub.3                                                                             H      CH.sub.3                                                                            CH.sub.3                                                                            N    O                                       H      CH.sub.3                                                                             H      CH.sub.3                                                                            OCH.sub.3                                                                           N    O                                       H      CH.sub.3                                                                             H      OCH.sub.3                                                                           OCH.sub.3                                                                           N    O                                       H      C.sub.2 H.sub.5                                                                      H      OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O                                       H      C.sub.2 H.sub.5                                                                      H      CH.sub.3                                                                            OCH.sub.3                                                                           CH   O                                       H      C.sub.2 H.sub.5                                                                      H      OCH.sub.3                                                                           CH.sub.3                                                                            N    O                                       5-F    CH.sub.3                                                                             H      OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O                                       6-Cl   CH.sub.3                                                                             H      OCH.sub.3                                                                           CH.sub.3                                                                            CH   O                                       4-Br   CH.sub.3                                                                             H      OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O                                       3-CH.sub.3                                                                           CH.sub.3                                                                             H      OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O                                       5-CF.sub.3                                                                           CH.sub.3                                                                             H      OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O                                       5-OCH.sub.3                                                                          CH.sub.3                                                                             H      OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O                                       H      CH.sub.3                                                                             CH.sub.3                                                                             OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O                                       ______________________________________                                    

                  TABLE IIIb                                                      ______________________________________                                         ##STR141##                                                                   R.sub.1                                                                            R.sub.6 R.sub.13                                                                             X      Y     Z    W"   m.p. (°C.)                  ______________________________________                                        H    CH.sub.3                                                                              H      CH.sub.3                                                                             CH.sub.3                                                                            CH   O                                       H    CH.sub.3                                                                              H      OCH.sub.3                                                                            OCH.sub.3                                                                           CH   O                                       H    CH.sub.3                                                                              H      CH.sub.3                                                                             OCH.sub.3                                                                           CH   O                                       H    CH.sub.3                                                                              H      CH.sub.3                                                                             CH.sub.3                                                                            N    O                                       H    CH.sub.3                                                                              H      OCH.sub.3                                                                            OCH.sub.3                                                                           N    O                                       H    CH.sub.3                                                                              H      OCH.sub.3                                                                            CH.sub.3                                                                            N    O                                       H    C.sub.2 H.sub.5                                                                       H      OCH.sub.3                                                                            OCH.sub.3                                                                           CH   O                                       H    C.sub.2 H.sub.5                                                                       H      CH.sub.3                                                                             OCH.sub.3                                                                           CH   O                                       H    C.sub.2 H.sub.5                                                                       H      CH.sub.3                                                                             CH.sub.3                                                                            CH   O                                       H    C.sub.2 H.sub.5                                                                       H      OCH.sub.3                                                                            OCH.sub.3                                                                           N    O                                       H    C.sub.2 H.sub.5                                                                       H      CH.sub.3                                                                             OCH.sub.3                                                                           N    O                                       H    H       H      OCH.sub.3                                                                            OCH.sub.3                                                                           CH   O                                       H    H       H      OCH.sub.3                                                                            CH.sub.3                                                                            CH   O                                       H    H       H      CH.sub.3                                                                             CH.sub.3                                                                            CH   O                                       H    H       H      OCH.sub.3                                                                            OCH.sub.3                                                                           N    O                                       H    H       H      OCH.sub.3                                                                            CH.sub.3                                                                            N    O                                       H    CH.sub.3                                                                              CH.sub.3                                                                             OCH.sub.3                                                                            OCH.sub.3                                                                           CH   O                                       H    CH.sub.3                                                                              CH.sub.3                                                                             CH.sub.3                                                                             OCH.sub.3                                                                           N    O                                       ______________________________________                                    

                  TABLE IIIc                                                      ______________________________________                                         ##STR142##                                                                                                                   m.p.                          R.sub.1                                                                           R.sub.6                                                                              R.sub.12                                                                             R.sub.13                                                                           X     Y        Z    W"   (°C.)                  ______________________________________                                        H   H      H      H    CH.sub.3                                                                            CH.sub.3 CH   O    198-                                                                          202°                   H   H      H      H    CH.sub.3                                                                            OCH.sub.3                                                                              CH   O    214-                                                                          217°                   H   H      H      H    OCH.sub.3                                                                           OCH.sub.3                                                                              CH   O    228-                                                                          231°                   H   H      H      H    CH.sub.3                                                                            CH.sub.3 N    O    220-                                                                          224°                   H   H      H      H    OCH.sub.3                                                                           OCH.sub.3                                                                              N    O    202-                                                                          210°                   H   H      H      H    CH.sub.3                                                                            OCH.sub.3                                                                              N    O    200-                                                                          204°                   H   CH.sub.3                                                                             CH.sub.3                                                                             H    OCH.sub.3                                                                           OCH.sub.3                                                                              CH   O                                  H   CH.sub.3                                                                             CH.sub.3                                                                             H    OCH.sub.3                                                                           CH.sub.3 CH   O                                  H   CH.sub.3                                                                             CH.sub.3                                                                             H    CH.sub.3                                                                            CH.sub.3 CH   O                                  H   CH.sub.3                                                                             CH.sub.3                                                                             H    CH.sub.3                                                                            OCH.sub.3                                                                              N    O                                  H   C.sub.2 H.sub.5                                                                      CH.sub.3                                                                             H    CH.sub.3                                                                            OCH.sub.3                                                                              CH   O                                  H   C.sub.2 H.sub.5                                                                      CH.sub.3                                                                             H    OCH.sub.3                                                                           OCH.sub.3                                                                              CH   O                                  H   C.sub.2 H.sub.5                                                                      CH.sub.3                                                                             H    OCH.sub.3                                                                           CH.sub.3 N    O                                  H   C.sub.2 H.sub.5                                                                      CH.sub.3                                                                             H    CH.sub.3                                                                            CH.sub.3 CH   O                                  H   H      H      CH.sub.3                                                                           OCH.sub.3                                                                           OCH.sub.3                                                                              CH   O                                  H   H      H      H    OCH.sub.3                                                                           CH.sub.2 OCH.sub.3                                                                     CH   O                                  H   H      H      H    CH.sub. 3                                                                           OC.sub.2 H.sub.5                                                                       N    O                                  H   H      H      H    OCH.sub.3                                                                           CH(OCH.sub.3).sub.2                                                                    CH   O                                  H   H      H      H    CH.sub.3                                                                            C.sub.2 H.sub.5                                                                        CH   O                                  H   H      H      H    Cl    NH.sub.2 CH   O                                  H   H      H      H    Cl    NHCH.sub.3                                                                             CH   O                                  H   H      H      H    Cl    N(CH.sub.3).sub.2                                                                      CH   O                                  H   H      H      H    Cl    OCH.sub.3                                                                              CH   O                                  H   CH.sub.3                                                                             CH.sub.3                                                                             H    OCH.sub.3                                                                           OCH.sub.3                                                                              N    O                                  H   H      H      CH.sub.3                                                                           OCH.sub.3                                                                           CH.sub.3 N    O                                  H   H      H      CH.sub.3                                                                           OCH.sub.3                                                                           CH.sub.3 CH   O                                  H   CH.sub.3                                                                             CH.sub.3                                                                             H    CH.sub.3                                                                            CH.sub.3 N    O                                  ______________________________________                                    

                  TABLE IIId                                                      ______________________________________                                         ##STR143##                                                                                                                   m.p.                          R.sub.1                                                                             R.sub.6 R.sub.12                                                                             R.sub.13                                                                           X     Y     Z    W"   (°C.)                  ______________________________________                                        H     H       H      H    CH.sub.3                                                                            CH.sub.3                                                                            CH   O                                  H     H       H      H    OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O                                  H     H       H      H    CH.sub.3                                                                            OCH.sub.3                                                                           CH   O                                  H     H       H      H    CH.sub.3                                                                            CH.sub.3                                                                            N    O                                  H     H       H      H    OCH.sub.3                                                                           OCH.sub.3                                                                           N    O                                  H     H       H      H    CH.sub.3                                                                            OCH.sub.3                                                                           N    O                                  H     H       H      CH.sub.3                                                                           OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O                                  H     H       CH.sub.3                                                                             H    CH.sub.3                                                                            CH.sub.3                                                                            CH   O                                  H     H       CH.sub.3                                                                             H    OCH.sub.3                                                                           CH.sub.3                                                                            CH   O                                  H     H       CH.sub.3                                                                             H    OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O                                  H     H       CH.sub.3                                                                             H    CH.sub.3                                                                            CH.sub.3                                                                            N    O                                  H     H       CH.sub.3                                                                             H    OCH.sub.3                                                                           OCH.sub.3                                                                           N    O                                  H     H       CH.sub.3                                                                             H    OCH.sub.3                                                                           CH.sub.3                                                                            N    O                                  H     CH.sub.3                                                                              CH.sub.3                                                                             H    OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O                                  H     CH.sub.3                                                                              CH.sub.3                                                                             H    OCH.sub.3                                                                           CH.sub.3                                                                            CH   O                                  H     CH.sub.3                                                                              CH.sub.3                                                                             H    CH.sub.3                                                                            CH.sub.3                                                                            CH   O                                  H     CH.sub.3                                                                              CH.sub.3                                                                             H    OCH.sub.3                                                                           OCH.sub.3                                                                           N    O                                  H     CH.sub.3                                                                              CH.sub.3                                                                             H    OCH.sub.3                                                                           CH.sub.3                                                                            N    O                                  H     C.sub.2 H.sub.5                                                                       CH.sub.3                                                                             H    OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O                                  H     C.sub.2 H.sub.5                                                                       CH.sub.3                                                                             H    OCH.sub.3                                                                           CH.sub.3                                                                            N    O                                  H     C.sub.2 H.sub.5                                                                       CH.sub.3                                                                             H    OCH.sub.3                                                                           CH.sub.3                                                                            CH   O                                  5-F   H       H      H    OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O                                  6-Cl  H       H      H    OCH.sub.3                                                                           OCH.sub.3                                                                           CH   O                                  4-Br  H       H      H    OCH.sub.3                                                                           CH.sub.3                                                                            CH   O                                  3-CH.sub.3                                                                          H       H      H    OCH.sub.3                                                                           CH.sub.3                                                                            CH   O                                  H     H       H      CH.sub.3                                                                           OCH.sub.3                                                                           CH.sub.3                                                                            CH   O                                  H     H       H      CH.sub.3                                                                           OCH.sub.3                                                                           CH.sub.3                                                                            N    O                                  H     CH.sub.3                                                                              CH.sub.3                                                                             H    CH.sub.3                                                                            CH.sub.3                                                                            N    O                                  ______________________________________                                    

                  TABLE IV                                                        ______________________________________                                         ##STR144##                                                                   Q           R.sub.1                                                                             R.sub.13                                                                             W"   X.sub.1                                                                             G    m.p. (°C.)                    ______________________________________                                         ##STR145## H     H      O    CH.sub.3                                                                            O                                          ##STR146## H     H      O    CH.sub.3                                                                            O                                          ##STR147## H     H      O    Cl    O                                          ##STR148## H     H      O    CH.sub.3                                                                            O                                          ##STR149## H     H      O    OCH.sub.3                                                                           O                                          ##STR150## H     H      O    CH.sub.3                                                                            O                                          ##STR151## H     H      O    CH.sub.3                                                                            O                                          ##STR152## H     H      O    CH.sub.3                                                                            O                                          ##STR153## H     H      O    OCH.sub.3                                                                           CH.sub.2                                   ##STR154## H     H      O    CH.sub.3                                                                            O                                          ##STR155## H     H      O    CH.sub.3                                                                            CH.sub.2                                   ##STR156## H     H      O    Cl    CH.sub.2                                  ______________________________________                                    

                  TABLE V                                                         ______________________________________                                         ##STR157##                                                                   Q           R.sub.1 R.sub.13                                                                             W"    X.sub.1                                                                             m.p. (°C.)                      ______________________________________                                         ##STR158## H       H      O     CH.sub.3                                      ##STR159## H       H      O     Cl                                            ##STR160## H       H      O     OCH.sub.3                                     ##STR161## H       H      O     CH.sub.3                                      ##STR162## H       H      O     CH.sub.3                                      ##STR163## H       H      O     CH.sub.3                                     ______________________________________                                    

                  TABLE VI                                                        ______________________________________                                         ##STR164##                                                                   Q           R.sub.1 R.sub.13                                                                             W"    X.sub.1                                                                             m.p. (°C.)                      ______________________________________                                         ##STR165## H       H      O     CH.sub.3                                      ##STR166## H       H      O     Cl                                            ##STR167## H       H      O     OCH.sub.3                                     ##STR168## H       H      O     CH.sub.3                                      ##STR169## H       H      O     CH.sub.3                                      ##STR170## H       H      O     CH.sub.3                                     ______________________________________                                    

                  TABLE VII                                                       ______________________________________                                         ##STR171##                                                                                                             m.p.                                Q           R.sub.1                                                                             R.sub.13 X.sub.2  Y.sub.2                                                                             (°C.)                        ______________________________________                                         ##STR172## H     H  O     CH.sub.3 OCH.sub.3                                  ##STR173## H     H  O     C.sub.2 H.sub.5                                                                        OCH.sub.3                                  ##STR174## H     H  O     CH.sub.2 CH.sub.2 CH.sub.3                                                             OCH.sub.3                                  ##STR175## H     H  O     CH.sub.2 CF.sub.3                                                                      OCH.sub. 3                                 ##STR176## H     H  O     CH.sub.3 OC.sub.2 H.sub.5                           ##STR177## H     H  O     CH.sub.3 OCH.sub.3                                  ##STR178## H     H  O     CH.sub.3 SCH.sub.3                                  ##STR179## H     H  O     CH.sub.3 OCH.sub.3                                  ##STR180## H     H  O     CH.sub.3 SC.sub.2 H.sub.5                           ##STR181## H     H  O     CH.sub.3 OCH.sub.3                                  ##STR182## H     H  O     CH.sub.2 CF.sub.3                                                                      SCH.sub.3                                  ##STR183## H     H  O     CH.sub.3 OCH.sub.3                                 ______________________________________                                    

Formulations

Useful formulations of the compounds of Formula I can be prepared inconventional ways. They include dusts, granules, pellets, solutions,suspensions, emulsions, wettable powders, emulsifiable concentrates andthe like. Many of these may be applied directly. Sprayable formulationscan be extended in suitable media and used at spray volumes of from afew liters to several hundred liters per hectare. High strengthcompositions are primarily used as intermediates for furtherformulation. The formulations, broadly, contain about 0.1% to 99% byweight of active ingredient(s) and at least one of (a) about 0.1% to 20%surfactant(s) and (b) about 1% to 99.9% solid or liquid inertdiluent(s). More specifically, they will contain these ingredients inthe following approximate proportions:

                  TABLE VIII                                                      ______________________________________                                                    Active  Weight Percent*                                                       Ingredient                                                                            Diluent(s)                                                                              Surfactant(s)                                   ______________________________________                                        Wettable Powders                                                                            20-90      0-74     1-10                                        Oil Suspensions,                                                                             3-50     40-95     0-15                                        Emulsions, Solutions,                                                         (including Emulsifiable                                                       Concentrates)                                                                 Aqueous Suspension                                                                          10-50     40-84     1-20                                        Dusts          1-25     70-99     0-5                                         Granules and Pellets                                                                        0.1-95      5-99.9  0-15                                        High Strength 90-99      0-10     0-2                                         Compositions                                                                  ______________________________________                                         *Active ingredient plus at least one of a Surfactant or a Diluent equals      100 weight percent.                                                      

Lower or higher levels of active ingredient can, of course, be presentdepending on the intended use and the physical properties of thecompound. Higher ratios of surfactant to active ingredient are sometimesdesirable, and are achieved by incorporation into the formulation or bytank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook ofInsecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books,Caldwell, New Jersey, but other solids, either mined or manufactured,may be used. The more absorptive diluents are preferred for wettablepowders and the denser ones for dusts. Typical liquid diluents andsolvents are described in Marsden, "Solvents Guide," 2nd Ed.,Interscience, New York, 1950. Solubility under 0.1% is preferred forsuspension concentrates; solution concentrates are preferably stableagainst phase separation at 0° C. "McCutecheon's Detergents andEmulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, as wellas Sisely and Wood, "Encyclopedia of Surface Active Agents", ChemicalPublishing Co., Inc., New York, 1964, list surfactants and recommendeduses. All formulations can contain minor amounts of additives to reducefoaming, caking, corrosion, microbiological growth, etc.

The methods of making such compositions are well known. Solutions areprepared by simply mixing the ingredients. Fine solid compositions aremade by blending and, usually, grinding as in a hammer or fluid energymill. Suspensions are prepared by wet milling (see, for example,Littler, U.S. Pat. No.3,060,084). Granules and pellets may be made byspraying the active material upon preformed granular carriers or byagglomeration techniques. See J. E. Browning, "Agglomeration", ChemicalEngineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer'sHandbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.

For further information regarding the art of formulation, see forexample:

H. M. Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, line 16through Col. 7, line 19 and Examples 10 through 41;

R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Mar. 14, 1967, Col. 5, line43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58,132, 138-140, 162-164, 166, 167 and 169-182;

H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, Col. 3,line 66 through Col. 5, line 17 and Examples 1-4;

G. C. Klingman, "Weed Control as a Science", John Wiley & Sons, Inc.,New York, 1961, pp. 81-96; and

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., BlackwellScientific Publications, Oxford, 1968, pp. 101-103.

In the following examples, all parts are by weight unless otherwiseindicated.

EXAMPLE 28

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        2-(isoxazol-5-yl)-N--[(4,6-dimethoxypyrimidin-2-yl)-                                                      80%                                               aminocarbonyl]benzenesulfonamide                                              sodium alkylnaphthalenesulfonate                                                                          2%                                                sodium ligninsulfonate      2%                                                synthetic amorphous silica  3%                                                kaolinite                   13%                                               ______________________________________                                    

The ingredients are blended, hammer-milled until all the solids areessentially under 50 microns, reblended, and packaged.

EXAMPLE 29

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        2-(isoxazol-5-yl)-N--[(4-methoxy-6-methylpyrimidin-2-                                                      50%                                              yl)aminocarbonyl]benzenesulfonamide                                           sodium alkylnaphthalenesulfonate                                                                           2%                                               low viscosity methyl cellulose                                                                             2%                                               diatomaceous earth           46%                                              ______________________________________                                    

The ingredients are blended, coarsely hammer-milled and then air-milledto produce particles essentially all below 10 microns in diameter. Theproduct is reblended before packaging.

EXAMPLE 30

    ______________________________________                                        Granule                                                                       ______________________________________                                        Wettable Powder of Example 29                                                                         5%                                                    attapulgite granules   95%                                                    (U.S.S. 20-40 mesh; 0.84-0.42 mm)                                             ______________________________________                                    

A slurry of wettable powder containing 25% solids is sprayed on thesurface of attapulgite granules in a double-cone blender. The granulesare dried and packaged.

EXAMPLE 31

    ______________________________________                                        Extruded Pellet                                                               ______________________________________                                        N--[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-                                                       25%                                                (1- and/or 2-methyl-1H--pyrazol-3-yl)benzene-                                 sulfonamide                                                                   anhydrous sodium sulfate   10%                                                crude calcium ligninsulfonate                                                                             5%                                                sodium alkylnaphthalenesulfonate                                                                          1%                                                calcium/magnesium bentonite                                                                              59%                                                ______________________________________                                    

The ingredients are blended, hammer-milled and then moistened with about12% water. The mixture is extruded as cylinders about 3 mm diameterwhich are cut to produce pellets about 3 mm long. These may be useddirectly after drying, or the dried pellets may be crushed to pass aU.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S.No. 40 sieve (0.42 mm openings) may be packaged for use and the finesrecycled.

EXAMPLE 32

    ______________________________________                                        Oil Suspension                                                                ______________________________________                                        N--[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-                                                       25%                                                (1-methyl-1H--pyrazol-4-yl)benzenesulfonamide                                 polyoxyethylene sorbitol hexaoleate                                                                       5%                                                highly aliphatic hydrocarbon oil                                                                         70%                                                ______________________________________                                    

The ingredients are ground together in a sand mill until the solidparticles have been reduced to under about 5 microns. The resultingthick suspension may be applied directly, but preferably after beingextended with oils or emulsified in water.

EXAMPLE 33

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        N--[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino-                                                       20%                                                 carbonyl]-2-(1- and/or 2-methyl-1H--pyrazol-3-yl)-                            benzenesulfonamide                                                            sodium alkylnaphthalenesulfonate                                                                        4%                                                  sodium ligninsulfonate    4%                                                  low viscosity methyl cellulose                                                                          3%                                                  attapulgite               69%                                                 ______________________________________                                    

The ingredients are thoroughly blended. After grinding in a hammer-millto produce particles essentially all below 100 microns, the material isreblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) andpackaged.

EXAMPLE 34

    ______________________________________                                        Low Strength Granule                                                          ______________________________________                                        N--[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino-                                                       1%                                                  carbonyl]-2-(1-methyl-1H--pyrazol-4-yl)benzene-                               sulfonamide                                                                   N,N--dimethylformamide    9%                                                  attapulgite granules      90%                                                 (U.S.S. 20-40 sieve)                                                          ______________________________________                                    

The active ingredient is dissolved in the solvent and the solution issprayed upon dedusted granules in a double cone blender. After sprayingof the solution has been completed, the blender is allowed to run for ashort period and then the granules are packaged.

EXAMPLE 35

    ______________________________________                                        Aqueous Suspension                                                            ______________________________________                                        N--[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-                                                        40%                                               (isoxazol-4-yl)benzenesulfonamide                                             polyacrylic acid thickener  0.3%                                              dodecylphenol polyethylene glycol ether                                                                   0.5%                                              disodium phosphate           1%                                               monosodium phosphate        0.5%                                              polyvinyl alcohol           1.0%                                              water                       56.7%                                             ______________________________________                                    

The ingredients are blended and ground together in a sand mill toproduce particles essentially all under 5 microns in size.

EXAMPLE 36

    ______________________________________                                        Solution                                                                      ______________________________________                                        2-(isoxazol-4-yl)-N--[(4-methoxy-6-methylpyrimidin-                                                       5%                                                2-yl)aminocarbonyl]benzenesulfonamide, sodium                                 salt                                                                          water                      95%                                                ______________________________________                                    

The salt is added directly to the water with stirring to produce thesolution, which may then be packaged for use.

EXAMPLE 37

    ______________________________________                                        Low Strength Granule                                                          ______________________________________                                        2-(isoxazol-4-yl)-N--[(4-methoxy-6-methyl-1,3,5-                                                          0.1%                                              triazin-2-yl)aminocarbonyl]benzenesulfonamide                                 attapulgite granules       99.9%                                              (U.S.S. 20-40 mesh)                                                           ______________________________________                                    

The active ingredient is dissolved in a solvent and the solution issprayed upon dedusted granules in a double-cone blender. After sprayingof the solution has been completed, the material is warmed to evaporatethe solvent. The material is allowed to cool and then packaged.

EXAMPLE 38

    ______________________________________                                        Granule                                                                       ______________________________________                                        2-(isoxazol-5-yl)-N--[(4,6-dimethoxypyrimidin-2-yl)-                                                     80%                                                aminocarbonyl]benzenesulfonamide                                              wetting agent               1%                                                crude ligninsulfonate salt (containing                                                                   10%                                                5-20% of the natural sugars)                                                  attapulgite clay            9%                                                ______________________________________                                    

The ingredients are blended and milled to pass through a 100 meshscreen. This material is then added to a fluid bed granulator, the airflow is adjusted to gently fluidize the material, and a fine spray ofwater is sprayed onto the fluidized material. The fluidization andspraying are continued until granules of the desired size range aremade. The spraying is stopped, but fluidization is continued, optionallywith heat, until the water content is reduced to the desired level,generally less than 1%. The material is then discharged, screened to thedesired size range, generally 14-100 mesh (1410-149 microns), andpackaged for use.

EXAMPLE 39

    ______________________________________                                        High Strength Concentrate                                                     ______________________________________                                        N--[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-                                                        99%                                               (1-methyl-1H--pyrazol-4-yl)benzenesulfonamide                                 silica aerogel              0.5%                                              synthetic amorphous silica  0.5%                                              ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produce amaterial essentially all passing a U.S.S. No. 50 screen (0.3 mmopening). The concentrate may be formulated further if necessary.

EXAMPLE 40

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        N--[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-                                                        90%                                               (1- and/or 2-methyl-1H--pyrazol-3-yl)benzene-                                 sulfonamide                                                                   dioctyl sodium sulfosuccinate                                                                             0.1%                                              synthetic fine silica       9.9%                                              ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produceparticles essentially all below 100 microns. The material is siftedthrough a U.S.S. No. 50 screen and then packaged.

EXAMPLE 41

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        2-(isoxazol-5-yl)-N--[(4-methoxy-6-methylpyrimidin-                                                      40%                                                2-yl)aminocarbonyl]benzenesulfonamide                                         sodium ligninsulfonate     20%                                                montmorillonite clay       40%                                                ______________________________________                                    

The ingredients are thoroughly blended, coarsely hammer-milled and thenair-milled to produce particles essentially all below 10 microns insize. The material is reblended and then packaged.

EXAMPLE 42

    ______________________________________                                        Oil Suspension                                                                ______________________________________                                        N--[(4-methoxy-6-methyl-1,3,5-triazin-2-yl))amino-                                                        35%                                               carbonyl]-2-(1- and/or 2-methyl-1H--pyrazol-3-                                yl)benzenesulfonamide                                                         blend of polyalcohol carboxylic                                                                            6%                                               esters and oil soluble petroleum                                              sulfonates                                                                    xylene                      59%                                               ______________________________________                                    

The ingredients are combined and ground together in a sand mill toproduce particles essentially all below 5 microns. The product can beused directly, extended with oils, or emulsified in water.

EXAMPLE 43

    ______________________________________                                        Dust                                                                          ______________________________________                                        N--[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino-                                                         10%                                               carbonyl]-2-(1-methyl-1H--pyrazol-4-yl)benzene-                               sulfonamide                                                                   attapulgite                 10%                                               Pyrophyllite                80%                                               ______________________________________                                    

The active ingredient is blended with attapulgite and then passedthrough a hammer-mill to produce particles substantially all below 200microns. The ground concentrate is then blended with powderedpyrophyllite until homogeneous.

Utility

The compounds of the present invention are powerful herbicides. Theyhave utility for broad-spectrum pre- and/or post-emergence weed controlin areas where complete control of all vegetation is desired, such asaround fuel storage tanks, ammunition depots, industrial storage areas,parking lots, drive-in theaters, around billboards, highway and railroadstructures. Alternatively, the subject compounds are useful for theselective pre- or post-emergence weed control in crops, such as wheat,barley, rice, soybeans and corn.

The rates of application for the compounds of the invention aredetermined by a number of factors, including their use as selective orgeneral herbicides, the crop species involved, the types of weeds to becontrolled, weather and climate, formulations selected, mode ofapplication, amount of foliage present, etc. In general terms, thesubject compounds should be applied at levels in the range of about 0.01to 2 kg/ha, the lower rates being suggested for use on lighter soilsand/or those having a low organic matter content, for selective weedcontrol or for situations where only short-term persistence is required.

The compounds of the invention may be used in combination with any othercommercial herbicide examples of which are those of the triazine,triazole, uracil, urea, amide, diphenylether, carbamate and bipyridyliumtypes.

The herbicidal properties of the subject compounds were discovered in anumber of greenhouse tests. The test procedures and results follow.

Test A

Seeds of crabgrass (Digitaria sp.), barnyard-grass (Echinochloacrusgalli), wild oats (Avena fatua), sicklepod (Cassia obtusilfolia),morningglory (Ipomoea sp.), cocklebur (Xanthium sp.), sorghum, corn,soybean, rice, wheat and nutsedge tubers (Cyperus rotundus) were plantedin a growth medium and treated pre-emergence with a non-phytotoxicsolvent solution of the compounds of Table A. At the same time, cottonhaving five leaves (including cotyledonary ones), bush beans with thethird trifoliolate leaf expanding, crabgrass, barnyardgrass and wildoats with two leaves, sicklepod with three leaves (includingcotyledonary ones), morningglory and cocklebur with four leaves(including the cotyledonary ones), sorghum and corn with four leaves,soybean with two cotyledonary leaves, rice with three leaves, wheat withone leaf, and nutsedge with three-five leaves were sprayed with anon-phytotoxic solvent solution of the compounds of Table A. Othercontainers of the above-mentioned weeds and crops were treated pre- orpost-emergence with the same non-phytotoxic solvent so as to provide asolvent control. A set of untreated control plants was also included forcomparison. Pre-emergence and post-emergence treated plants and controlswere maintained in a greenhouse for sixteen days, then all treatedplants were compared with their respective controls and rated visuallyfor response to treatment.

The following rating system was used:

O=no effect;

10=maximum effect;

C=chlorosis or necrosis;

D=defoliation;

E=emergence inhibition;

G=growth retardation;

H=formative effects;

I=increased chlorophyl;

P=terminal bud kill;

S=albinism;

U=unusual pigmentation;

X=axillary stimulation;

6F=delayed flowering; and

6Y=abscised buds or flowers.

The ratings are summarized in Table A. The compounds tested are highlyactive herbicides. Certain of the compounds have utility for weedcontrol in wheat. ##STR184##

    TABLE A       Cmpd. 1 Cmpd. 2 Cmpd. 3 Cmpd. 4 Cmpd. 5 Cmpd. 6 Cmpd. 7 Cmpd. 8 Cmpd.     9 Cmpd. 10 Rate kg/ha .05 .05 0.4 .05 0.4 .05 0.4 .05 .05 .05 0.4 .05     0.4 .05 0.05       POST-EMERGENCE Bush bean 9C 10C 9C 9C 9C 5C,9G,6Y 5C,9G,6Y 6C,9G,6Y 9C 9     C 9C 9C 0.4 9C 9C Cotton 9C 9C 6C,9G 6C,9G 6C,9G 5C,9G 6C,9G 6C,9G 6C,9G     9C 9C 6C,9G 9C 6C,9G 5C,9G Morningglory 4C,8G 10C 6C,9G 6C,9G 5C,9G     5C,9H 5C,9H 6C,9G 6C,9G 10C 10C 9C 6C,9G 9C 9C Cocklebur 9C 10C 9C 6C,9G     9C 5C,9H 5C,9H 10C 6C,9G 9C 9C 9C 9C 9C 9C Sicklepod 9C 9C 6C,9G 6C,9G     3C,5H 4C,5H 4C,9G 6C,9G 6C,9G 9C 10C 9C 6C,9G 6C,9G 9C Nutsedge 6C,9G     4C,8G 6C,9G 6C,9G 2G 0 6C,9G 5C,9G 9C 8C 10C 10C 6C,9G 1C,5G 5C,9G     Crabgrass 2C,6G 2C,8G 2C,9G 5G 2C,8G 1C 3C,8G 2C,5H 2C,7H 2C,6G 3C,8G     3C,7H 3C,8G 2C,7G 9G Barnyardgrass 9C 9C 9C 4C,9H 10C 9C 10C 10C 9C     6C,9H 9C 9C 9C 10C 9C Wild Oats 8G,5X 3C,9G 2C,9G 2C,9G 2C 0 3C,9H 2C,5G     2C,9G 2C 3C,9G 2C,5G 5C,9G 2C,8G 9C Wheat 2C,7G 3C,9G 2U,9G 3C,9G 0 0     2C,9G 2C,3G 3C,9G 0 4C,9G 2C,8G 1C 0 5C,9G Corn 5U,9G 5U,9G 5U,9G 3U,9G     7U,9C 5C,9G 5C,9G 5C,9G 9C 5U,9G 9C 5U,9G 7U,9C 5U,9C 10C Soybean 9C 9C     6C,9G 9C 3C,9G 3C,9G 5C,9G 6C,9G 9C 9C 9C 9C 9C 2C,9G 9C Rice 5C,9G     6C,9G 5C,9G 5C,9G 1C,3G 0 6C,9G 5C,9G 5C,9G 2C,7G 6C,9G 4C,9G 4C,9G     3C,9G 6C,9G Sorghum 3U,9G 3U,9G 4U,9G 1U,9G 3C,9H 2C,9G 1C,9H 9H 4U,9C     3C,8G 4U,9C 4U,9G 6U,9G 2C,9G 9C Sugar beet               9C PRE-EMERGENC     E Morningglory 3C,9G 9C 3C,9G 9G 3C,9G 9G 2C,9H 3C,9G 9C 10C 9C 1C,9H 9C 1     C,9H 10H Cocklebur 9H 9H 9H 9H 3C,9H 8H 9H 2C,9H 9H 9H 9H 9H -- -- 5C,9H     Sicklepod 3C,9G 3C,9G 3C,9G 5C,8G 3C,7H 2C,5H 2C,9G 3C,9H 5C,9G 9C 9C     3C,9G 9C 7C,9G 9H Nutsedge 10E 10E 10E 10E 0 0 10E 10E 10E 1C,6G 10E 10E     5C,9G 6G 3C,9H Crabgrass 2C,5G 2C,8G 2C,6G 1C,3G 1C 0 3C,9G 2C,6G 2C,9G     1C,3G 2C,9G 2C,7H 4C,8G 2C,5G 4C,8G Barnyardgrass 5C,9H 6C,9H 9H 2C,9H     2C,9H 2C,6H 6C,9H 5C,9H 5C,9H 2C,7H 9C 5C,9H 9C 3C,9H 10E Wild Oats     2C,9G 5C,9G 2C,9G 2C,9H 1C 0 3C,9G 2C,9G 3C,9G 2C,6G 2C,9H 2C,9G 3C,9H     3C,8G 5C,8G Wheat 2C,9G 2C,9G 9H 2C,9G 0 0 1C,9G 2C,9G 2C,9H 2C 9H 2C,9G     3G 0 2C,8G Corn 2U,9G 9G 2C,9G 2C,9G 2C,9G 9G 5C,9G 2C,9G 5C,9G 1C,9G 9C     3C,9G 3C,9H 2C,8H 9C Soybean 9H 9H 9H 2C,8H 9H 2C,5H 9H 8H 9H 9H 9H     2C,8H 9H 3C,7H 9C Rice 10E 10E 10E 2C,9H 2C,5G 2C,3G 10E 5C,9H 10E 5G     10E 5C,9H 10E 3C,8G 9G Sorghum 2C,9G 9H 10H 2C,9H 2C,9H 2C,9H 2C,9H     2C,8H 7C,9H 1C,6H 7C,9H 2C,9H 2C,9H 9G 10E Sugar beet     10E     Cmpd. 11 Cmpd. 12 Cmpd. 13 Cmpd. 14 Cmpd. 15 Cmpd. 16 Cmpd. 17     Cmpd. 18 Cmpd. 19 Cmpd. 20  Cmpd. 21 Cmpd. 22 Cmpd. 23 Cmpd. 24 Cmpd. 25     Rate kg/ha 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05     0.05 0.05 0.05       POST-EMERGENCE Bush bean 9C 9C 6C,9G,6Y 9C 9C 9C 9C 9C 4C,9G,6Y 9C     6C,9G,6Y 9C 9C 9c 5C,9G,6Y Cotton 4C,9G 5C,9G 4C,8G 5C,9G 4C,9G 4C,9G     4C,9G 4C,9G 3C,4G 6C,9G 4C,9G 4C,9G 5C,9G 6C,9G 4C,9G Morningglory 10C     10C 4C,8H 5C,9G 4C,9G 3C,8G 9C 5C,9G 3C,4H 5C,9G 5C,9G 5C,9G 5C,9G 9C     5C,9G Cocklebur 10C 10C 5C,9H 10C 5C,9G 3C,9H 9C 10C 2C,8H 9C 10C 9C 10C     10C 10C Sicklepod 9C 9C 3H,5C 9C 5C,9G 3C,7H 4C,9G 5C,9G 1C 5C,9G 5C,9G     9C 3C,8G 6C,9G 3C,7G Nutsedge 10C 6C,9G 3C,9G 10C 9C 4C,9G 5C,9G 4C,9G     2C,7G 9C 9C 10C 2C,6G 4C,8G 5C,9G Crabgrass 5C,9G 9C 2C,5G 5C,9G 2C,9G     3C,8G 1C 0 0 3C,8G 2C,8G 6C,9G 3G 0 2C,5G Barnyardgrass 9C 9C 5C,9G 9C     9C 5C,9H 3C,6H 0 0 5C,8H 6C,9H 9C 2C,5H 1C,4H 3C,8H Wild Oats 9C 9C     5C,9H 2C,9G 6C,9G 5C,9H 2C 0 0 2C 3C,9H 9C 1C 1C 1C,4G Wheat 9C 9C 0     1C,6G 9C,9G 2C,8G 0 0 0 1C 1C,7G 1C,9G 1C 1C,3G 1C,2G Corn 10C 9C 5U,9G     5U,9H 6U,9G 4C,9G 3C,9H 3C,9H 1C,4G 2U,9G 5U,9G 9C 1U,9H 2U,9H 3U,9G     Soybean 9C 9C 1C,2G 5C,9G 5C,9G 4C,9G 5C,9G 5C,9G 4H 4C,8G 4C,9G 2C,8H     5C,9G 2C,8G 3C,9G,5X Rice 6C,9G 6C,9G 5C,9G 5C,9G 5C,9G 5C,9G 6G 1C,2G     3G 4C,8G 5C,9G 5C,9G 4G 1C,5G 5C,9G Sorghum 10C 10C 5C,9G 2U,9G 5C,9G     2C,9G 9G 1C,8H 2G 3U,9G 5C,9G 9C 1C,5H 2C,6H 2U,9G Sugar beet 9C 9C     5C,8G 9C 9C 5C,9G 9C 9C 4G 9C 9C 9C 9C 9C 9C PRE-EMERGENCE Morningglory     9C 9G 2C,3H 9C 9C 9H 9C 9C 2C,9H 9C 5C,9G 2C,9G 5C,9G 9C 9G Cocklebur 9H     9G 9G 9H 9H 9H 9H 9H 8H -- 9H 9H 8H 9H -- Sicklepod 9G 9G 1C 5C,9G 9C 8H     5C,9G 4C,9G 3H 3C,9G 2C,9G 2C,9G 3C,9G 3C,9G 5C,9G Nutsedge 10E 10E 0     10E 10E 10E 10E 10E 0 10E 10E 10E 10E 7G 2C,7G Crabgrass 6C,9G 5C,9G 3G     2C,4G 3C,7G 1C,4G 1C 0 0 2C 2C,5G 2C,5G 1C 0 1C,2G Barnyardgrass 6C,9G     5C,9G 3C,7G 5C,9H 5C,9H 3C,8H 2G 2C 0 5C,9H 5C,9H 5C,9H 3C,5H 2C,6G     2C,5H Wild Oats 6C,9H 5C,9H 6H 5C,9G 5C,9G 2C,9H 1C 0 0 7G 2C,9G 3C,9H 0     1C,3G 3C,8H Wheat 5C,9H 4C,9G 2G 5C,9G 5C,9G 2C,9G 0 0 0 5G 1C,9G 2C,9H     0 0 1C,7G Corn 10H 5C,9G 4C,7G 4C,9G 10E 3C,9H 3C,9H 9H 2C,7H 2C,9G     2C,9G 10E 3C,8G 2C,9H 2C,9H Soybean 9H 3C,6H 1C 9H 9H 8H 2C,9H 9H 2C,2H     2C,2H 2C,6H 2C,5H 3C,4H 3C,4H 3C,3H Rice 10E 10E 2C,5G 10E 10E 10E 3C,6G     2C,4G 2C,4G 10E 5C,9H 10E 2C,6G 3C,7G 10E Sorghum 10H 6C,9H 2C,8H 10H     10H 3C,9H 4C,9H 2C,8H 3H 5C,9H 5C,9H 5C,9H 2C,7H 2C,8H 2C,9H Sugar beet     10E 10E 5G 10E 10E 5C,9G 9C 5C,9G 7G 5C,9G 10E 5C,9G 9C 10E 6C,9G        Cmpd. 26 Cmpd. 27 Cmpd. 28 Cmpd. 29 Cmpd. 30 Cmpd. 31 Cmpd. 32 Cmpd.     33 Cmpd. 34 Cmpd. 35 Cmpd. 36 Cmpd. 37 Cmpd. 38 Cmpd. 39 Cmpd. 40 Rate     kg/ha 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05     0.05 0.4       POST-EMERGENCE Bush bean  9C 9C 9C 9C 9C 6C,9G,6Y 4C,9G,6Y 6C,9G,6Y     5C,9G,6Y 3C,9G,6Y 4C,9G,6Y 5C,9G,6Y 4C,5G,6Y 6C,9G,6Y 6C,6G,6Y Cotton     5C,9C 5C,9G 9C 5C,9G 9C 5C,9G 4C,9G 6C,9G 4C,9G 3C,9G 4C,9G 4C,9G 2C,5G     3C,8G 4C Morningglory 10C 10C 10C 10C 2C,8G 5C,9G 2C,7G 9C 5C,9G 4C,9G     5C,9G 5C,9G 4C,8G 4C,8H 3C,7H Cocklebur 10C 3C,9G 10C 9C 9C 5C,9G 5C,9G     6C,9G 5C,9G 3C,8H 4C,9H 4C,9G 2C,2H 4C,8H 3C Sicklepod 9C 5C,9G 9C 5C,9G     5C,9G 4C,8H 4C,7H 4C,8H 5C,8H 4C,8H 4C,8H 4C,6H 2C,2H 5C 4C Nutsedge     5C,9G 2C,6G 6G 1C,5G 9G 2C,8G 4G 8G 9G 1C 1C,9G 2C,9G 5G 0 0 Crabgrass     4C,9G 1C,5G 6G 3C,8G 4C,8G 1C,5G 2C,6G 5C,9G 3C,9G 1C,3G 1C,6G 8G 1C,4G     1C 1C,3G Barnyardgrass 10C 2C,9H 5C 3C,9H 9C 5C,9H 5C,9H 5C,9H 5C,9G     4C,9H 4C,9H 5C,8H 5C,8H 4C,7H 2C,8H Wild Oats 6C,9G 0 1C 2C,9H 9C 9G     2C,9G 4C,9G 4C,9H 0 2C,9H 4C,9G 2C 0 2C Wheat 6C,9G 0 4G 8G 6C,9G 9G 3G     2C,9G 9G 0 2C,9G 2C,9G 1C,5G 0 1C Corn 3U,9C 3C,9G 3U 4U,9C 2U,8G 9G     3U,9G 2C,8G 2C,9G 3C,9H 2C,9H 2C,9H 0 2C,8H 2C,9H Soybean 4C,8G 9C 9C 9C     9C 9C 6C,9G 5C,9G 9C 4C,9G 2C,8H 4C,9G 3C,8G 3C,8G 3C,7G,7X Rice 5C,9G     1C,7G 4C 5C,9G 5C,9G 4C,9G 4C,9G 5C,9G 6C,9G 1C,4G 4C,9G 4C,8G 3C,8G 0     3C,9G Sorghum 5C,9G 2C,7H 2C 1C,9G 4C,9G 2C,9G 1C,9G 2C,9H 4C,9G 2C,7H     9G 4C,9G 3C,7H 2C,5H 3C,8H Sugar beet -- -- -- -- 5C,9G 5C,9G 4C,9G     4C,9G 2C,8G 4C,9G 3C,8H 2C,7G 2C,5G 3C,8G 4C,7G PRE-EMERGENCE Morningglor     y 9H 9H 9C 9G 7G 9G 1C 9G 9C 9G 2C,7C 9C 2C,4G 3C,8H 3C,7H Cocklebur 9H     9H 9H 9H 9H 2C,3H 1C 9H 9H 9H -- 9H 0 3C,9H 0 Sicklepod 9G 9G 9G 9G 9G     2C,2H 4C,6H 2C,8G 3C,8G 2C,7G 1C 2C,5G 2C 3C 0 Nutsedge 10E 10E 9G 9G     10E 9G 0 10E 10E 7G 7G 8G 4G 1C 0 Crabgrass 2C,8G 2C 2C 2C,5G 1C,7G 2C 0     3C,8G 2C,8G 2C 1C 2C,7G 2G 0 1G Barnyardgrass 5C,9H 2C,5H 2C,7H 10H 9H     3C,9H 3C,7H 5C,9H 5C,9H 3C,8H 2C,5G 4C,9H 2C,4G 2C,5G 2C Wild Oats 5C,9H     2C 2C,6G 10H 4C,9H 8G 2C,7H 4C,8G 4C,8G 0 2C 4C,8G 2G 1C,3G 0 Wheat     5C,9H 0 4G 9H 1C,9H 8G 1C,5G 3C,9G 3C,9G 0 1C 2C,9G 3G 1C,2G 0 Corn 10H     3C,9G 2C,9G 3U,9H 9H 3C,9G 1C,8G 9H 3C,9G 2C,5G 2C,5G 2C,9G 1C 4C,8G     3C,6H Soybean 9H 9H 8H 8H 9H 2C,8H 1C 8H 3C,7H 0 0 3C,6H 0 4C,3H 2C Rice     10E 4C,9H 5C,9H 10E 10E 3C,8H 5C,9H 4C,9H 3C,9H 0 3C,8H 3C,9H 1C 0 2C     Sorghum 10H 1C,6G 4C,8H 2C,9H 5C,9H 4C,9H 3C,8G 5C,9H 4C,9H 1C,4G 2C,8H     5C,9H 2C,5G 3C,5G 2C,3G Sugar beet 10E 10E 10E 10E 10E 4C,9G 10E 10E     4C,9G 10E 3C,6G 2C,7G 0 3C,7G 2G        Cmpd.                 40 Cmpd. 41 Cmpd. 42 Cmpd. 43 Cmpd. 44 Cmpd. 45     Cmpd. 46 Cmpd. 47 Cmpd. 48 Cmpd. 49 Cmpd. 50 Cmpd. 51 Cmpd. 52 Cmpd. 53     Cmpd. 54 Cmpd. 55 Rate kg/ha 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05     0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05       POST-EMERGENCE Bush bean 1C 4C,9G,6Y 6C,9G,6Y 6C,9G,6Y 1C 9C 9D,9G,6Y     2C,9H,6Y 9C  9C 5C,9G,6Y 6C,9G,6Y 9C 9C 9C 5S,9G,6Y Cotton 1C 5C,9G     4C,8H 4C,4H 0 5C,9G 6C,9G 6C,9G 5C,9H 5C,9G 4C,8H 4C,8G 9C 5C,9G 6C,9G     5C,9G Morningglory 4C 5C,9G 3C 2C,2H 0 5C,9G 5C,9G 5C,9G 5C,9H 9C 4C,9H     2C,8G 9C 5C,9G 10C 9C Cocklebur 1C 5C,9G 3C 1C 0 5C,9G 5C,9G 4C,9G 10C     8G 3C,9G 10C 9C 9C 9C 9C Sicklepod 1C 5C,9G 2C 2C,5G 0 9C 5C,9G 4C,8H     5C,9G 4C,9G 3C,4H 4C,8H 9C 5C,9G 9C 4C,6G Nutsedge 0 2C,5G 0 0 0 10C     5C,9G 4C,9G 5G 9G 2C 6C,9G 10C 6C,9G 5C,9G 2C,8G Crabgrass 0 1C,4G 1C 0     0 2C,7G 8G 3C,5H 0 0 0 1C,5G 6C 3C,7G 3C,8G 3C,7G Barnyardgrass 1C 4C,8H     2C 1C 0 9C 5C,9H 3C,7H 0 0 0 5C,9H 9C 9C 5C,9H 10C Wild Oats 0 2C,9G 0 0     0 2C,6G 3C,9G 2C,9G 1C 0 0 1C,3G 2C 2C,9G 5G,5X 2C,9H Wheat 0 3C,9G 0 0     0 0 1C 1C,3G 0 0 0 0 9G 1C,7G 4G 8G Corn 1C 2C,9G 2C,8H 2C 0 3U,9G 2U,9H     3C,8H 2C,8H 6G 2C,2H 9C 4U 1U,9H 2U,9G 5C,9G Soybean 1C 4C,8H 2C,5H     2C,2H 0 5C,9G 5C,9G 5C,9G 5C,9G 4C,9G 2C,9G 4C,9G 5C 5C,9G 9C 6C,9G Rice     1C 5C,9G 2C 1C 0 2C,9G 5C,9G 5C,9G 4G 0 6G 8G 5C 6C,9G 4C,9G 5C,9G     Sorghum 1C 5C,9G 2C 3C,4G 0 9H 5C,9G 3C,9G 2C,8H 4C 0 5U,9G 5U 3C,9G     2C,9G 5C,9G Sugar beet 1C -- -- -- -- 5C,9G 9C 3C,8G 9C 9C 9C 9C 9C 9C     -- -- PRE-EMERGENCE Morningglory 0 8H 0 0 0 9C 9C 9H 9C 9C 2C,8H 8G 9C     9G 9C 2C,9G Cocklebur 2G 8H 0 0 0 9H 9H 9H 9H 2C,8H 2C,7G 9H 9H 9H 9H 9H     Sicklepod 0 2C 0 0 0 5C,9G 5C,9G 2C,9G 9C 5C,9G 2C,7G 8G 2C,9G 2C,9G 9G     2C,8G Nutsedge 3G 0 0 0 0 10E 9G 2C,8G 0 7G 3G 2C,9G 10E 10E 10E 10E     Crabgrass 3G 0 2G 2G 0 1C,3G 2C 1C 0 0 0 0 2C,3G 1C,5G 2C,7G 3C,6G     Barnyardgrass 1C 1C 2H 1C 0 4C,9H 2C,8H 2C 0 0 0 2C,7H 3C,9G 5C,9H 2C,9G     3C,9H Wild Oats 0 1C,3G 0 0 0 3C,5G 2C,9G 3C,9G 0 0 0 1C 2C,9G 2C,8H     2C,6G 3C,9H Wheat 0 4G 0 0 0 0 1C,7G 4G 0 0 0 1C 2C,8G 8G 6G 2C,9H Corn     1C 4C,7G 1C 2C,5G 0 9H 5C,9H 3C,9H 2C,8H 3C,8H 2C,4G 5C,9H 9H 2C,8H     2C,9H 5C,9H Soybean 0 1C,1H 0 0 0 9H 9H 3C,7H 2C,8H 9H 2C,4H 4C,7H 9H     3C,5H 9H 9H Rice 1C 3C,5H 0 0 0 5C,9H 5C,9H 4C,9G 3C,4G 1C 2C,4G 5C,8G     10E 10E 10E 9H Sorghum 1C 3C,6G 0 1C 0 9C 9C 4C,9H 2C,9H 2C,7H 3G 2C,9H     10H 5C,9H 10E 6C,9H Sugar beet 0 -- -- -- -- 10E 5C,9G 3C,9H 9C 5C,9G     2C,6H 4C,8G 4C,9G 10E -- --

Test B

Two plastic bulb pans were filled with fertilized and limed Fallsingtonsilt loam or Woodstown sandy loam soil. One pan was planted with corn,sorghum, Kentucky bluegrass and several grassy weeds. The other pan wasplanted with cotton, soybeans, purple nutsedge (Cyperus rotundus), andseveral broadleaf weeds. The following grassy and broadleaf weeds wereplanted: crabgrass (Digitaria sanguinalis), barnyardgrass (Echinochloacrusgalli), wild oats (Avena fatua), johnsongrass (Sorghum halepense),dallisgrass (Paspalum dilatatum), giant foxtail (Setaria faberii),cheatgrass (Bromus secalinus), mustard (Brassica arvensis), cocklebur(Xanthium pensylvanicum), pigweed (Amaranthus retroflexus), morningglory(Ipomoea hederacea), sicklepod (Cassia obtusifolia), teaweed (Sidaspinosa), velvetleaf (Abutilon theophrasti), and jimsonweed (Daturastramonium). A 12.5 cm diameter plastic pot was also filled withprepared soil and planted with rice and wheat. Another 12.5 cm pot wasplanted with sugar beets. The above four containers were treatedpre-emergence with several test compounds within the scope of theinvention.

Twenty-eight days after treatment, the plants were evaluated andvisually rated for response to the chemical treatments utilizing therating system described previously for Test A. The data are summarizedin Table B. Note that the compounds are highly active herbicides, andthat several of them have utility for selective weed control in cropssuch as wheat or soybeans (e.g., see Compound Nos. 22, 23 and 24).

    TABLE B       PRE-EMERGENCE ON FALLSINGTON SILT LOAM SOIL                  Com-            pound  Compound 1 Compound 2 Compound 3     Compound 4 Compound 5 Compound 6 Compound 7 Compound 8 Compound 9     Compound 10 11 Rate kg/ha 0.03 0.12 0.03 0.12 0.12 0.03 0.25 0.06 0.03     0.12 0.12 0.03 0.015 0.12 0.03 0.12 0.03 0.12 0.03 0.015 0.06 0.015       Crabgrass 5G 6G 7G 7G 0 0 4G 0 2G 7G,3H 4G,2H 2G 0 0 0 2G 2G 3G 0 8G     9G Barnyardgrass 7G 10C 10C 10C 8G,9C 2G 9G,7C 6G,3H 9G,5H 9G,9C 9G,9C     9G,5H 5G,5C 4G 2G 9G,9C 4G,2H 9G,8C 3G,3H 9G 9G,9C Sorghum 8G,5H 10C 10E     10E -- -- -- -- -- -- -- -- 6G,3H -- -- -- -- -- -- 10C 10C 10C Wild     Oats 5G 5G 7G,3H 7G,3H 0 0 2G 0 0 0 6G,3H 5G,3H 2G 0 0 0 0 0 0 7G 9G,9C     8G Johnsongrass 7G,5H 9G,8C 9G,8C 9G,9C 7G,3H 4G 6G,3H 3G 5G,3H 8G,5H     7G,3H 6G,3H 6G 0 0 2G 3G 6G,3H 3G,3H 8G 9G,9C 8G Dallisgrass 6G 6G 8G,3H     8G,3H 0 0 3G 0 0 0 8G,3H 5G 2G 0 0 4G 4G 0 0 6G 9G 8G Giant foxtail 6G     8G,8C 9G,9C 10C 4G,5H 0 6G,3H 0 6G,3H 7G,5H 7G,5H 5G,3H 3G 0 0 5G,3H     4G,3H 0 0 8G 9G,9C 9G Ky. bluegrass 8G,5C 9G,9C 8G,9C 10C 10C 7G,5C     7G,7C 2G 6G 10C 10C 8G,8C -- 7G,5C 0 10C 8G,8C 7G,5C 3G 8G 9G 9G     Cheatgrass 10E 10E 10E 10E 8G,8C 5G 7G 4G 6G,3C 8G,8C 10C 8G,8C 10C 3G 0     10C 8G,8C 5C,6G 0 9G 9G,9C 9G Sugar beets 10C 10E 10C 10C 6G,5H 2G 9G,9C     8G,7C 0 7G,7C 10C 8G,9C 7G,5H 10C 10C 10C 10C 10C 10C 9G 10C 10C Corn 3G     5G 7G,5H 8G,5H 2H,5G 0 10E 4G 4G,3H 9G,5H 9G,5H 5G,5H 7G 7G,5H 3G,2U     7G,5H 3G,2U 6G,5H 2U 7G 9G,9C 9G Mustard 10E 10E 10C 10C 10C 7G,5H 9G,8C     8G,5H 8G,5H 9G,9C 10C 9G,9C 9G,9C 10C 10C 10C 10C 10C 8G,9C 10C 10C 10C     Cocklebur 3G 5G 6G,3H 8G,5H 5G,3H 0 7G,7C 3G 0 3H 6G,5H 4G,3H 2G 9G,9C     4G,3H 7G,5H -- 4G 0 7G 8G 9G Pigweed 10E 10E 10E 10E 5G 0 9G,9C 7G 9G,9C     8G,8C 10C 8G,8C -- 10C 10C 10C 10C 10C 8G -- -- -- Nutsedge 6G 8G 8G 10E     8G 5G 4G 0 4G 5G 9G 7G 6G,3H 5G 0 9G 6G 3G 0 10C 10C 10C Cotton 7G 9G,9C     8G,3H 9G,8C -- 4G 5G,5H 2G 3G 5G,3H 7G,3H 5G 5G 9G,5H 6G,3H 8G,5H 3G     6G,5H 5G,3H 9G 9G 8G Morningglory 6G,3C 6G,3H 9G,8C 9G,9C 3H 0 8G,5H     6G,3H 3G 4G,3H 7G,3H 5G 0 10C 0 8G,5H 0 6G,5H 6G,5H 9G 9G 9G Sicklepod     7G 8G,8C 8G,5C 8G,5C 3H 0 5G,3H 3G 3G 3G 5G 3G 7G 9G,7C 6G,3H 7G 3G     7G,3H 2C 8G 9G 9G Teaweed 6G,3H 8G,8C 8G,8C 10C 5G,3H 0 6G,5H 2C 2G     6G,3H 9G,9C 6G,3H 9G 9G,9C 3G 7G,3H 4G,3H 3G,2C 0 8G 9G 8G Velvetleaf     7G,5H 10C 9G,9C 10C 7G,5H 0 6G,5H 3C 3G 8G,5H 7G,5H 2G 9G 9G,9C 4G,3H     9G,9C 3H,4G 6G,5H 2C,4G 9G 9G 9G Jimsonweed 6G 8G,7C 10C 10C 0 0 4G 0 3G     8G,3H 8G,7C 3H,5G 3G 10C 5G 4G 3G 9G,8C 3G 9G 9G,9C 9G Soybean 4G,2H     7G,5H 5G,5H 8G,8C 5G,5H 0 8G,5H 6G,5H 2G 5G,4H 7G,5H 5G,3H 6G 9G,9C     6G,5H 5G,4H 3G 3G,2H 3G 7G 7G,7H 7G Rice 7G 8G,8C 7G,5C 9G,9C 6G,3H 3G     5G 0 7G 9G,5H 10C 8G,5H 7G 7G,3H 0 8G,8C 7G,3H 7G,3H 3G 10C 10C 10C     Wheat 5G 5G 7G 8G,6C 5G 3G 0 0 0 3G 7G 3G 3G 3G 0 4G 2G 0 0 6G 6G     7G       Com-            pound 11 Compound 12 Compound 20 Compound 21     Compound 22 Compound 23 Compound 24 Compound 26 Compound 27 Compound 28     Compound 29  Compound 30 Rate kg/ha  0.06 0.015 0.06 0.03 0.12 0.03 0.12 0     .03 0.12 0.03 0.12 0.03 0.12 0.12 0.03 0.12 0.03 0.12  0.03 0.12 0.03     0.12 0.03       Crabgrass 8G 3G 5G 5G 5G 6G 7G 5G 7G 0 4G 0 5G 9G 9G 5G 5G 5G 4G 8G 5G     8G 4G Barnyardgrass 9G,9C 9G 9G,9C 8G 9G 9G 9G 8G 9G 3G 6G 3G 7G 9G,9C     9G,9C 6G 5G 6G 5G 9G 7G 9G,9C 8G Sorghum 10C 10C 10C 9G 9G 10C 10C 9G     10C 7G 8G 8G 9G 10C 10C 8G 5G 10C 9G 10C 10C 10C 10C Wild Oats 9G,9C 8G     8G 0 4G 7G 9G 7G 9G 0 0 0 3G 8G 8G 4G 3G 4G 3G 8G 7G 9G 8G Johnsongrass     8G 8G 9G,9C 7G 9G 9G 9G 9G 9G 8G 10C 0 5G 9G,9C 8G 0 0 0 0 4G 3G 9G 9G     Dallisgrass 9G 9G 9G 7G 8G 7G 9G 7G 9G 0 0 0 2G 10C 10C 2G 0 0 0 2G 0     10C 9G Giant foxtail 9G,9C 8G 9G,9C 8G 8G 9G 9G 7G 9G 0 0 0 6G 10C 10C     2G 0 2G 0 8G 6G 10C 9G Ky. bluegrass 9G 9G 9G,9C 8G 9G 9G 9G 9G 9G 0 0     4G 6G 10C 10C 3G 2G 6G 2G 8G 6G 10C 9G Cheatgrass 9G,9C 9G 9G,9C 9G 10C     10C 10C 9G 10C 2G 5G 2G 7G 10C 10C 8G 2G 10C 8G 10C 10C 10C 10C Sugar     beets 10C 10C 10C 9G 10C 9G 10C 9G 10C 10C 10C 10C 10C 10C 10C 10C 10C     10C 10C 10C 10C 10C 10C Corn 8G,7H 8G 9G,9C 8G 9G 9G 10C 9G 10C 5G 8G 8G     9G 10C 10C 6G,5H 3G 9G 4G 10C 9G 10C 10C Mustard 10C 10C 10C 10C 10C 10C     10C 9G 10C 9G 10C 10C 10C 10C 10C 10C 10C 10C 10C 10C 10C 10C 9G     Cocklebur 9G 9G 9G 7G 7G -- 8G -- 8G 7G 7G 7G 9G 7H,8G 8G,7H 7G,5H 7G,3H     8G,7H 6G,2H 8G,7H 8G,7H 9G 8G Pigweed -- -- -- -- -- -- -- -- -- -- --     -- -- -- -- -- -- -- -- -- -- -- -- Nutsedge 10C 10C 10C 10C 10C 10C 10C     10C 10C 8G 9G 7G 8G 10C 10C 9G 7G 9G 7G 9G 8G 10C 10C Cotton 9G 8G 9G 9G     9G 9G 9G 8G 9G 7G 9G 8G 9G 9G,9C 9G -- 9G -- 10C 9C,9G 8G 9G 6G Morninggl     ory 9G 7G 9G 8G 9G 9G 9G 9G 9G 9G 9G 9G 9G 9G 9G 9G 7G 8G 8G 8G 8G 7G 4G     Sicklepod 9G 6G 7G 9G 9G 9G 9G 6G 9G 6G 9G 9G 9G 9G 8G 9G 7G 8G 8G 9G 8G     9G 8G Teaweed 8G 8G 8G 6G 7G 7G 9G 8G 9G 7G 9G 9G 9G 9G 8G 7G 6G 7G 6G     6G 4G 9G 8G Velvetleaf 9G 9G 9G 9G 9G 9G 9G 9G 9G 8G 9G 9G 9G 9G 9G 8G     6G 9G 7G 8G 6G 9G 8G Jimsonweed 9G,9C 9G 9G 9G 9G 9G 9G 9G 9G 9G 9G 9G     9G 9G 9G 9G 7G 10C 9G 9G 8G 9G 9G Soybean 8G,7H 5G 8G,7H 3G 5G 3G 5G 2G     2G 2G 3G 3G 4G 9G 9G 9G 9G 9G 9G 9G 9G 8G,7H 6G,3H Rice 10C 10C 10C 9G     10C 9G 10C 10C 10C 5G 7G 5G 8G 10C 10C 9G 7G 10C 8G 10C 10C 10C 10C     Wheat 7G 7G 7G 0 0 0 2G 2G 7G 0 0 0 0 10C 9G 3G 2G 2G 2G 5G 3G 10C     9G        Compound 31 Compound 32 Compound 33 Compound 34 Compound 35     Compound 36 Compound 37 Compound 53 Compound 54 Compound 55 Rate kg/ha     0.12 0.03 0.12 0.03 0.12 0.03 0.12 0.03 0.12 0.03 0.12 0.03 0.12  0.03     0.12 0.03 0.12 0.03 0.015 0.12 0.03 0.015       Crabgrass 2G 0 5G 0 8G,3C 6G,3C 6G 3G 2G 0 0 0 5G 0 5G 2G 2G 0 0 5G 2G     0 Barnyardgrass 6G 3G 8G 4G 9G,9C 9G,9C 9G,9C 5G 6G 5G 5G 4G 8G 6G 9G 7G     8G,8C 7G,5H 6G,3C 7G,5C 5G 2G Sorghum 5G 2G 9G 4G,3H 9G 9G 9G 3G 7G,5H     3G 9G 6G,3H 10C 9G 9G,9C 9G,9C 10C 10C 10C 10C 9G,7H 8G,5H Wild Oats 4G     2G 9G 5G 9G 6G 8G 6G 5G 5G 3G 2G 7G 4G 6G 5G 4G 0 0 6G 4G 2G Johnsongrass      6G 5G 8G 7G 9G 8G 8G 7G 5G 4G 6G 3G 9G 8G 9G 9G 5H,6G 2G,3H 0 9G,8H     8G,7H 5G,5H Dallisgrass 0 0 0 0 9G 8G 9G 2G 0 0 0 0 8G 0 8G 5G 2G 0 0 6G     3G 0 Giant foxtail 2G 0 9G 4G 9G 9G 8G 0 0 0 0 0 9G 3G 8G 5G 7G 5G 4G     7G,5C 3G 3G Ky. bluegrass 3G 2G 9G 7G 10C 9G 9G 6G 3G 2G 4G 0 8G 3G 9G     8G 9G 8G 7G 9G,9C 7G 7G Cheatgrass 5G 2G 10C 8G 9G,9C 9G,9C 9G,9C 7G 3G     0 7G 0 9G,9C 8G,8C 10C 9G 9G 8G 8G 9G,9C 8G 8G Sugar beets 10C 10C 10C     9G 9G 7G 8G 5G 9G 8G 3G 2G 6G 4G 10C 9G 10C 9G,9C 9G 10C 8G 7G Corn 5G     3G 9G,9C 9G 8G,7H 8G,5H 9G,9C 4G 5G 2G 3G 2G 8G 3G 9G 4G 8G,5C 7G,5H 3G     8G,7H 6G,5H 2G,3C Mustard 9G 8G 9G 2G 10C 9G 9G 8G 8G 3G 0 0 10C 9G 10C     9G 9G,9C 9G,9C 9G,9C 10C 9G,9C 8G,8C Cocklebur 8G 5G 9G 2G 5G 3G 2G 0 --     -- 0 0 5G 3G 9G 6G 7G,7H 3G 0 6G,7H -- 5G,5H Pigweed -- -- -- -- -- --     -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- Nutsedge 9G 8G 9G 8G 9G     8G 9G 6G 7G 4G 0 0 9G 6G 10C 10C 10C 10C 10C -- 10C -- Cotton 9G 7G 8G     6G 8G 5G 5G 4G 8G 3G 0 0 5G 2G 8G 5G 8G,5H 6G 7G 6G,3C 4G 2G Morningglory      9G 6G 5G 5G 8G 4G 6G 2G 8G 2G 0 0 7G 3G 7G 5G 8G,7H 6G,7H 5G,5H 7G 4G     4G Sicklepod 9G 6G 8G 5G 2G 0 2G 0 5G 0 0 0 5G 0 8G 2G 6G,5H 5G,3H 3G 7G     3G 2G Teaweed 8G 6G 7G 5G 8G 6G 7G 5G 5G 5G 3G 0 7G 2G 9G 4G 7G 7G 6G     10C 8G 8G Velvetleaf 7G 3G 5G 0 5G 2G 6G 0 3G 0 0 0 5G 0 9G 9G 10C 10C     6G 8G 7G 3G Jimsonweed 9G 5G 9G 2G 9G 8G 7G 0 2G 0 0 0 8G 4G 9G,9C 5G 5G     4G 3G 3G 2G 2G Soybean 9G 8G,5H 9G 6G 7G,3C 5G 6G 2G 3G 2G 0 0 7G,5H     2G,2C 6G,7H 3G,5H 8G,5H 7G,5H 7G,3H 8G,7H 6G,7H 6G,5H Rice 7G 3G 10C 10C     10C 9G 10C 6G 7G 2G 9G 7G 9G 7G 10C 10C 10C 10C 8G 10C 9G 7G Wheat 2G 0     4G 0 9G 3G 9G 6G 0 0 0 0 8G 7G 3G 2G 2G 0 0 7G 4G 2G

Test C

Two ten-inch in diameter plastic pans lined with polyethylene linerswere filled with prepared Woodstown sandy loam soil. One pan was plantedwith seeds of wheat (Triticum aestivum), barley (Hordeum vulgare), wildoats (Avena fatua), downy brome (Bromus tectorum), cheatgrass (Bromussecalinus), blackgrass (Alopecurus myosuroides), annual bluegrass (Poaannua), green foxtail (Setaria viridis), quackgrass (Agropyron repens),Italian ryegrass (Lolium multiflorum) and ripgut brome (Bromus rigidus).The other pan was planted with seeds of Russian thistle (Salsola kali),tansy mustard (Descuraina pinnata), Galium aparine, tumble mustard(Sisymbrium altissium) kochia (Kochia scoparia), shepherd's purse(Capsella bursapastoris), Matricaria inodora, black nightshade (Solanumnigrum), yellow rocket (Barbarea vulgaris), wild mustard (Brassicakaber) or rapeseed and wild buckwheat (Polygonum convolvulus). SometimesVeronica persica was included among the test species. The above two panswere treated pre-emergence. At the same time two pans in which the aboveplant species were growing were treated post-emergence. Plant height atthe time of treatment ranged from 1-15 cm depending on plant species.

The compounds applied were diluted with a nonphytotoxic solvent andsprayed over-the-top of the pans. An untreated control and a solventalone control were included for comparison. The treatments weremaintained in the greenhouse for 20 days at which time the treatmentswere compared to the controls and the effects visually rated. Therecorded data are presented in Table C. It will be seen that thecompounds have utility for weed control in cereal crops, such as wheatand barley.

                                      TABLE C                                     __________________________________________________________________________              Compound 4       Compound 7        Compound 35                                Pre-Emergence                                                                          Post-Emergence                                                                        Pre-Emergence                                                                          Post-Emergence                                                                         Pre-Emergence                                                                          Post-Emergence          Rate kg/ha                                                                              0.01 0.03                                                                              0.01                                                                              0.03                                                                              0.015                                                                              0.06                                                                              0.015                                                                              0.06                                                                              0.015                                                                              0.015                                                                             0.06 0.015              __________________________________________________________________________    wheat     0    1G  0   5G  0    0   0    2G  0    0   0    0                  barley    0    2G  0   0   0    4G  0    1G  0    0   0    0                  wild oats 0    2G  0   0   2G   2G  0    0   0    0   0    0                  downy brome                                                                             1C   3G  2G  7G  4G   6G  4G   5G  3G   0   0    0                  cheatgrass                                                                              1C,2G                                                                              2C,6G                                                                             0   7G  2G   1C,3G                                                                             4G   5G  3G   0   0    0                  blackgrass                                                                              0    2C,4G                                                                             0   5G  1C,5G                                                                              2C,8G                                                                             1C,7G                                                                              1C,7G                                                                             2G   0   0    0                  annual bluegrass                                                                        0    4G  0   3G  5G   6G  6G   6G  4G   0   0    0                  green foxtail                                                                           2C,2G                                                                              2C,3G                                                                             0   0   1C,4G                                                                              1C,5G                                                                             6G   5G  0    0   --   --                 quackgrass                                                                              2G   3G  0   2G  --   --  5G   4G  0    0   2G   0                  Italian ryegrass                                                                        1C,2G                                                                              2G  0   2G  5G   1C,7G                                                                             5G   5G  5G   0   4G   0                  ripgut brome                                                                            1C,4G                                                                              1C,6G                                                                             0   6G  1C,3G                                                                              1C,6G                                                                             5G   4G  4G   0   2G   0                  Russian thistle                                                                         2G   4G  0   7C,6G                                                                             1C,2G                                                                              2C,5G                                                                             4C,8G                                                                              10C 0    0   8C,9G                                                                              --                 tansy mustard                                                                           4G   9G  8G  10C 2C,9G                                                                              1C,9G                                                                             7C,8G                                                                              10C --   --  10C  10C                Galium aparine                                                                          --   --  8G  5C,8G                                                                             7G   1C,8G                                                                             5G   3C,7G                                                                             2C,8G                                                                              2C,5G                                                                             7G   3C,8G              tumble mustard                                                                          7G   9G  10C 10C 2C,9G                                                                              5C,9G                                                                             5C,9G                                                                              10C 10C  3C,9G                                                                             9C,9G                                                                              10C                kochia    6G   7G  3G  2C,2G                                                                             5C,8G                                                                              7C,9G                                                                             --   --  3G   0   3C,3G                                                                              7G                 shepherd's purse                                                                        8G   8G  --  --  5C,9G                                                                              2C,9G                                                                             10C  9C,9G                                                                             8C,9G                                                                              8G  8G   3G                 Matricaria inodora                                                                      0    4G  7C,9G                                                                             9C,9G                                                                             1C,9G                                                                              3C,9G                                                                             7C,9G                                                                              8C,9G                                                                             8C,9G                                                                              8G  3C,8G                                                                              5G                 black nightshade                                                                        3G   5G  0   0   2G   1C,8G                                                                             1C,4G                                                                              10C 3C,9G                                                                              5G  7G   4G                 yellow rocket                                                                           2C,2G                                                                              3C,5G                                                                             --  --  2C,9G                                                                              2C,9G                                                                             2C,8G                                                                              2C,9G                                                                             7G   4G  4G   3G                 rapeseed  1C,3G                                                                              3C,7G                                                                             10C 10C 2C,8G                                                                              3C,9G                                                                             10C  10C 9G   5G  3C,9G                                                                              5G                 wild buckwheat                                                                          1C,3G                                                                              2C,6G                                                                             2C,8G                                                                             9C,9G                                                                             3C,8G                                                                              4C,9G                                                                             3C,7G                                                                              7C,9G                                                                             2C,8G                                                                              4G  8G   5G                 Veronica persica                                      3G   3G                 __________________________________________________________________________                   Compound 27      Compound 28    Compound 32                                   Pre-Emergence                                                                         Post-Emergence                                                                        Pre-Emergence                                                                         Post-Emergence                                                                        Pre-Emergence                                                                         Post-Emergence         Rate kg/ha     0.06                                                                              0.015                                                                             0.06                                                                              0.015                                                                             0.06                                                                              0.015                                                                             0.06                                                                              0.015                                                                             0.06                                                                              0.015                                                                             0.06                                                                              0.015              __________________________________________________________________________    wheat          0   0   1G  2G  1G  0   2G  2G  4G  0   1G  0                  barley         0   0   2G  2G  2G  0   3G  2G  5G  0   3G  0                  wild oats      3G  0   4G  3G  3G  3G  4G  2G  8G  4G  2G  3G                 downy brome    4G  2G  7G  4G  8G  5G  7G  5G  8G  2C,8G                                                                             7G  6G                 cheatgrass     4G  0   3G  4G  8G  3G  6G  4G  2C,7G                                                                             7G  5G  6G                 blackgrass     5G  0   3G  2G  3C,9G                                                                             5G  7G  5G  5C,9G                                                                             2C,7G                                                                             3C,8G                                                                             2C,7G              annual bluegrass                                                                             7G  3G  3G  2G  8C,9G                                                                             6G  8G  5C,9G                                                                             3C,8G                                                                             2C,8G                                                                             2C,7G                  green foxtail  5G  0   --  --  2C,8G                                                                             4G  --  --  7C,9G                                                                             3C,6G                                                                             --  --                 quackgrass     5G  0   4G  5G  7G  5G  4G  3G  8G  8G  10C 7G                 Italian ryegrass                                                                             5G  2G  6G  5G  2C,8G                                                                             6G  7G  5G  5C,9G                                                                             3C,8G                                                                             7C,9G                                                                             8G                 ripgut brome   7G  0   5G  4G  2C,8G                                                                             7G  6G  3G  8G  7G  7G  5G                 Russian thistle                                                                              2C,5G                                                                             2G  9C  9C  5C,8G                                                                             2C,5G                                                                             10C 10C 0   0   10C 10C                tansy mustard  8G  10C 10C 10C 10C 10C 10C 10C 10C --  10C 10C                Galium aparine 8G  6G  10C 10C 10C 4G  5G  5G  5G  2C,5G                                                                             7G  3G                 tumble mustard 10C 10C 10C 10C 10C 10C 10C 9G,9C                                                                             10C 9G  10C 9G,9C              kochia         7G  6G  2G  0   10C 9G  10C 10C 9G  0   9G,9C                                                                             10C                shepherd's purse                                                                             10C 10C 10C 10C 10C 10C 10C 10C 10C 8G  10C 10C                Matricaria inoda                                                                             9C,9G                                                                             8C,9G                                                                             10C 8C,8G                                                                             9G,9C                                                                             9C,9G                                                                             10C 10C 8G  6G  10C 8C,8G              black nightshade                                                                             8G  7G  5G  4G  8G  7G  10C 8G  5G  6G  9C,9G                                                                             5G                 yellow rocket  9G  2C,8G                                                                             4g  4G  10C 9C,9G                                                                             10C 10C 8G  5G  8G  10C                rapeseed       10C 5C,9G                                                                             9G,9C                                                                             8C,8G                                                                             8C,9G                                                                             9C,9G                                                                             10C 10C 8G  5G  10C 7C,8G              wild buckwheat 3C,9G                                                                             8G  10C 6G  3C,9G                                                                             3C,8G                                                                             10C 9C,9G                                                                             2C,9G                                                                             7G  9C,9G                                                                             9C,8G              Veronica persica       5G  0           10C 10C         5G  3G                 __________________________________________________________________________

Test D

The test chemicals, dissolved in a non-phytotoxic solvent, were appliedin an overall spray to the foliage and surrounding soil of selectedplant species. One day after treatment, plants were observed for rapidburn injury. Approximately fourteen days after treatment, all specieswere visually compared to untreated controls and rated for response totreatment. The rating system was as described previously for Test A. Thedata are presented in Table D.

All plant species were seeded in Woodstown sandy loam soil and grown ina greenhouse. The following species were grown in soil contained inplastic pots (25 cm diameter by 13 cm deep): soybeans, cotton, alfalfa,corn, rice, wheat, sorghum, velvetleaf (Abutilon theophrasti), sesbania(Sesbania exaltata), Sicklepod (Cassia obtusifolia), morningglory(Ipomoea hederacea), jimsonweed (Datura stramonium), cocklebur (Xanthiumpensylvanicum), crabgrass (Digitaria sp.), nutsedge (Cyperus rotundus),barnyardgrass (Echinochloa crusgalli), giant foxtail (Setaria faberii)and wild oats (Avena fatua). The following species were grown in soil ina paper cup (12 cm diameter by 13 cm deep): sunflower, sugar beets, andmustard or rape. All plants were sprayed approximately 14 days afterplanting. Additional plant species such as johnsongrass and bindweed aresometimes added to this standard test in order to evaluate unusualselectivity.

Several of the compounds tested by this procedure are useful forpost-emergence control of weeds in crops such as rice, wheat, soybeans(see Compound No. 22) and corn (see Compound Nos. 7 and 23).

    TABLE D      Compound 1 Compound 2 Compound 3 Compound 4 Compound 5 Compound 6 Rate     kg/ha 0.06 0.015 0.004 0.001 0.06 0.015 0.004 0.001 0.06 0.015 0.004     0.06 0.015 0.06  0.015 0.004 0.06 0.015 0.004       Soybeans 10G,8C 10G,5C 3C,9G 6G 10G,6C 10G,4C 3C,9G 9G,8C 10G,7C 9G,2C     7G 9G,4C 8G,2C 10G,6C 10G 6G,4C 9G 9G 9G Velvetleaf 10C 10C 10C 6G 10C     10C 10C 7G,3C 10C 9G,9C 8G 9G,2C 7G,6C 10C 10C 3C,5G 9G 8G 2G Sesbania     10C 10C 10C 10C 10C 10C 10C 9G 10C 10C 3C,7G 8G,2C 6G 10C 9G,2C 3C,5G     10C 10C 7G Sicklepod 10C 10C 9G 7G 10C 10C 9G 3G,4C 9G 8G,2C 6G 9G,2C     8G,2C 10G 9G 3C,4G 10G 3G,2C 0 Cotton 10C 10C 10C 8G 10C 10C 10C 8G     9G,6C 8G,2C 5G 8G,2C 8G,2C 9G,4C 8G,2C 3C,4G 10G,4C 8G,4C 4G,2C Morninggl     ory 9G,2C 10C 8G 4G 9G,2C 9G,2C 9G,6C 0 9G,7C 9G,4C 4G 8G,5C 5G,3C 10C     9G,2C 1C,2G 10G 9G,4C 4G Alfalfa 10C 10C 6C,8G 10C 10C 10C 10C 0 5G 5G     2G 7G,6C 7G,6C 9G,8C 7G,5C 3G,2C 4C,6G 5G 0 Jimsonweed 9G 10C 5G 3G 9G     9C,9G 7G 4G 6G 2G 1G 2C 0 4G 4G 1C 9G 5G 0 Cocklebur 9G 9G,8C 7G 3G 9G     10C 7G 4G 9G 9G 1C,4G 9G 8G 8G 8G 0 8G -- 3G,1C Corn 9G,8C 10C 7G,3H 1G     10C 10C 3H,9G 2H,5G 9G 1G,1H 0 7G,4U 6G,4U 8G,4C 8G 3G 9G,4C 9G,1U 7G,2H     Crabgrass 0 0 3G 0 0 0 6G 0 0 3G 2G 2G 0 -- 2G 0 9G,2C 6G 6G Rice 8G,5C     2C,3G 4G 2G 8G,7C 5G,6C 7G 6G 7G 6G,4C 3G 3G 2G,2C 6G,6C 5G 4G 6G,3C 5G     0 Nutsedge 10C 10C 9G 0 10C 10C 8G 1G 7G,3C 6G 7G 0 0 7G 4G 6G,7C 7G,3C     8G 2G Barnyardgrass 10C 10C 9G,9C 7G 10C 10C 9G 7G 7G,3C 6G,2C 0 8G 8G     8G,2C 8G,2C 3G 8G,2H 8G 4G,2H Wheat 4G 0 4G 0 6G,6C 2G,2C 3G 0 7G 5G 1G     0 0 6G 0 2G 6G 6G 0 Giant foxtail 9G,7C 9G,7C 3G 4G 9G,9C 5G,5C 8G 7G 6G     4G 4G 0 0 9G 5G,4C 5G 6G 4G 2G Wild Oats 3G 0 0 0 7G,2C 3G 0 2G 7G 4G,2C     0 0 0 5G 0 2G 6G 6G 0 Sorghum 7G,6C 5C,6G 8G 2G 10C 6G,7C 9G 6G 8G 7G 7G     6G 6G 6G 4G 3G,2C 8G 8G 1H,4G Sunflower 10C 10C 5G 4G 10C 10C 9G 6G,1H     10C 9G,7C 9C 10C 10C 10C 10P 2H,6C 9G,5C 9G,5C 6G,3H Mustard 10C 10C     9G,8C 9G,6C 10C 10C 9G,6C 7G 9G,8C 5G -- 9G 9G,4C 10C 6G,3C -- 10C 8G,6C     7G Johnsongrass 8G,5C 5G,5C 0 0 10C 10C 7G 5G 8G 4G 0 4G 4G 4G 4G 4G     8G,6U 8G,2U 3G Sugar beets 10C 9G,9C 9G 9G,6C 8G,8C 10C 9G 8G 8G 5G 2C     9G 9G,3C 9G,9C 8G 2C 9G,9C 8G 6G Bindweed 10C 8G 0 0 10C 6G 0 0 0 0 0 4G     0 8G 4G 1G 4G 0 3G Rape         -- -- 9C -- -- -- -- 4C,2G       Compound 7 Compound 8 Compound 9 Compound 20 Compound 21 Compound 22     Compound 23  Rate kg/ha 0.06 0.015 0.004 0.001 0.06 0.015 0.004 0.06     0.015 0.004 0.06 0.015 0.06 0.015  0.06 0.015 0.06 0.015        Soybeans 10G,4C 10G,2C 10C 9G,6C 9G,4C 10C 10G 10G,5C 8G 5G 10C 8G,6C     10C 7G,4C 7G,4C 3G 9G,7C 5G,1C Velvetleaf 8G,5C 7G,2C 8G 7G 10C 10C 10C     9G,5C 8G,2C 3G,4C 10C 10C 9G 9G 9G 9G 7G 9G Sesbania 10C 9G,4C 10C 10C     10C 10C 10C 10C 2C,8G 5G 10C 10C 10C 10C 10C 10C 10C 10C Sicklepod     10G,6C 10C 10G 6G 10C 10G 8G 9G 7G,5C 0 10C 9G 9G 9G 8G 9G 9G 9G Cotton     10G,7C 10C 8G 8G 10C 10C 9G,9C 10C 9G 2C,7G 10C 10C 10C 10C 10C 10C 9G     10C Morningglory 10C 9G,6C 8G 7G 10C 9G,4C 9G,4C 10G 9G,4U 4G 8C,7G     8G,7C 7G,6C -- 8G,7C 6G 10C 10C Alfalfa 8G,6C 8G 8G 8G 4C,8G 2C,7G 3G     7G,3C 6G,2C 4G 7G 7G 9C 6G,2C 7G 6G 9G 3G Jimsonweed 9G,2C 9G 9G 9G --     6G 3G 7G 3G 0 10C 9G --  9G 9G 9G 9G 9G Cocklebur 10C 7G 10C 9G 9G 8G 8G     8G 8G 5G 2G 3G 10C 9G 9G 9G 9G 4G Corn 6G 0 1H 0 8G,1H 7G,1H 0 9G 1H,7G     0 6G 0 8G 7G 7G,4C 8G 1G 0 Crabgrass 8G 3G 0 0 3G 2G 0 3G 2G 3G 9G 6G 9G     7G 9G 7G 7G 3G Rice 2G 0 0 0 5G 6C,6G 0 0 2G 0 4G 3G 6G 4G 9C 7C,8G 1C 0     Nutsedge 3G 0 0 0 8G,3C 8G 6G 0 0 0 10C 10C 10C 10C 9G 6G 4C,5G 1G     Barnyardgrass 0 0 0 0 8G,4C 8G 4G 8G 6G,2C 2C 7G 4G 5G 8G 7C,8G 7G 0 0     Wheat 0 0 0 0 7G 3G 2G 0 0 0 0 1G 5G 3G 4G 1G 0 0 Giant foxtail 0 0 0 0     9G 8G 7G 4G 4G 4G 4G 4G 9G 8G 9G 9G 3G 0 Wild Oats 0 0 0 0 4G 4G 0 4G 2G     0 0 3G 2G 3G 8G 4G 0 0 Sorghum 0 0 0 0 7G 6G 4G 7G 4G 0 8G 8G 8G 9G 8G     8G 0 0 Sunflower 10C 10P 10C 10C 10P 10C 10C 9G,5C 9G,3C 3C,5G 9G 9G 10C     10C 10C 10C 10C 10C Mustard 10C 10C 10C 9G 9G,8C 7G,7C 6G,5C 7G,6C 7G,6C     4G,3C -- -- -- -- -- -- -- -- Johnsongrass 0 0 0 0 4G 6G 3G 3G 3G 0 6G     2G 10C 7G 10C 9G 2G 1G Sugar beets 10C 10C 9G 10C 9G 1H,9G 8G 8G 8G 7G     9G 10C 9G 9G 10C 10C 10C 10C Bindweed 0 0 9G -- 7G 8G 0 6G 6C 0 10C     4C,5G 4G 8G 3G 0 9G 7G Rape       9G 10C 10C 9C 10C 10C 9C 10C       Compound 24 Compound 41 Cmpd. 54 Compound 55 Rate kg/ha 0.06 0.015     0.06 0.015 0.015 0.06 0.015 0.004 0.001       Soybeans 9C 7G,2C 10C 9C 10C 10C 10C 6G,7C 7G,4C Velvetleaf 10C 9G 8G     7G 9G 10C 10C 6G 4G Sesbania 10C 10C 8G 7G 10C 10C 10C 4G 3G Sicklepod     9G 8G 9G 8G 8G 8G 4G 7G -- Cotton 10C 10C 10C 10C 8G 8C 9G 9G 9G     Morningglory 10C 9C 6G,4C 4G 10C 8G 8G -- 6G Alfalfa 4G 6G 7G 4G 10C 8C     4C,9G 7G 6G Jimsonweed 9G 9G 8G 9G 9G 6C,5G 4G,5C 4G 3G Cocklebur 7G 5G     10C 10C 7G 10C 6G 5G 3G Corn 7G 2G 7C 4G 7G 9G 3C,8G 4G 1G Crabgrass 2G     2G 2G 3G 2G 4G 0 0 0 Rice 4G 1G 3C,6G 1G 1G 2G,6C 3C 2G 0 Nutsedge 2G 0     9C 1G 8C 4G,4C 3G -- 2G Barnyardgrass 3G 0 1G 0 8G 8G 7G 3G 0 Wheat 1G 0     5G 3G 0 5G 4G 1G 0 Giant foxtail 5G 0 9G 6G -- 7G 6G 3G 1G Wild Oats 0 0     8G 7G 0 7G 7G 4G 2G Sorghum 0 0 8G 7G 8G 8G 8G 8G 6G Sunflower 10C 10C     6G 3G 10C 9G 4G 8G 4G Mustard ---- -- -- -- -- -- -- -- Johnsongrass 0     7G 8G 4G 0 3C 2G,1C 0 0 Sugar beets 10C 10C 10C 10C 7G 9G 9C 9G 9G     Bindweed 10C 7G 5G 1G 4G 9G 9G 8G 6G Rape  10C 10C 8G 10C 10C 10C 8C     6G

Test E

This test was designed to evaluate the potential utility of compoundsfrom within the scope of the invention for selective weed control inrice. The crop was transplanted into simulated paddies containing soiland propagules of barnyardgrass (Echinochloa sp.), water chestnut(Eleocharis sp.), and arrowhead (Sagittaria sp.). Three days aftertransplanting, the test chemicals were applied to the paddy water in anon-phytotoxic solvent at the rates shown in Table E. The paddies weremaintained in a greenhouse, and plant response ratings were takenseveral weeks after application utilizing the rating system as describedfor Test A. Several of the compounds tested have potential utility forselective weed control in rice.

                  TABLE E                                                         ______________________________________                                                  Plant Response                                                      Cmpd.  Rate              Barnyard-                                                                             Water  Arrow-                                No.    (g/ha)   Rice     grass   Chestnut                                                                             head                                  ______________________________________                                        1      0.5      0         9E     3G     3G                                            1       2C        7E     7G     10G                                           2       2G       10E     10C    3G                                            4       5G,2C    10E     10G,3C 7G                                            5       3G       6F,4E   10C    5G                                           20       10G,5C   10E     10C    10C                                   2      10       9G,2C    10E     7G     10G                                          40       10G,5C    9C     8G,3C  10E                                   7      25       0         4G     --     9G                                           100      0         4G     8G     10G,3C                                8       5       0         9C     --     5G,3H                                        20       5I       10C     10C    8G,2C                                 5       5       0         9C     3G     2G,2H                                        10       5G        8C     6G     5G,3H                                        20       7G       10C     9G     9G                                           40       9G,3C    10C     9G,2C  9G                                    35     10       0         8C     6G     0                                            40       0        10C     9G     9G,3H                                 ______________________________________                                    

What is claimed is:
 1. A compound of the formula ##STR185## where Q is##STR186## W" is O or S; W is O, S or NR;W' is O or S; R is H or C₁ -C₄alkyl; R₁ is H, F, Cl, Br, CH₃, CF₃ or OCH₃ ; R₂ is H, CH₃, C₂ H₅, Cl orBr; R₃ is H, CH₃, C₂ H₅, Cl, Br, OCH₃, OC₂ H₅ or SCH₃ ; R₄ is H or C₁-C₄ alkyl; R₅ is H, CH₃, C₂ H₅, Cl, Br, OCH₃, OC₂ H₅ or SCH₃ ; R₆ is H,CH₃ or C₂ H₅ ; R₇ is H or C₁ -C₄ alkyl; R₁₂ is H or CH₃ ; R₁₂ ' is H orCH₃ ; R₁₃ is H or CH₃ ; R₁₄ is H, CH₃, C₂ H₅, Cl, OCH₃, OC₂ H₅ or SCH₃ ;R₁₅ is C₁ -C₃ alkyl; A is ##STR187## X is CH₃ or OCH₃ ; Y is CH₃, C₂ H₅,CH₂ OCH₃, OCH₃, OC₂ H₅, CH(OCH₃)₂, NH₂, NHCH₃, N(CH₃)₂, OCH₂ CH₂ OCH₃,OCH₂ CF₃, SCH₃, CF₃ or ##STR188## Z is N; and their agriculturallysuitable salts; provided that (a) when R₂ is Cl or Br, then W is O or S;(b) when W" is S, then R₁₃ is H, and Y is CH₃, OCH₃, C₂ H₅, OC₂ H₅, CH₂OCH₃, CH(OCH₃)₂ or ##STR189## (c) when Q is ##STR190## then one of R₂ orR₃ must be H, CH₃ or C₂ H₅ ; (d) when Q is ##STR191## then one of R₂ orR₅ must be H, CH₃ or C₂ H₅ ; (e) the total number of carbon atoms of Qmust be less than or equal to
 8. 2. Compounds of claim 1 whereR and R₁₅are independently C₃ or C₂ H₅ ; R₂, R₃, R₄, R₅, R₆, R₇ and R₁₄ areindependently H or CH₃ ; and W" is O.
 3. Compounds of claim 2 where R₁and R₁₃ are H.
 4. Compounds of claim 3 where Y is CH₃, CH₂ OCH₃, OCH₃,OC₂ H₅, CH(OCH₃)₂ or ##STR192##
 5. Compounds of claim 4 where Q is##STR193##
 6. Compounds of claim 4 where Q is ##STR194##
 7. Compounds ofclaim 4 where Q is ##STR195##
 8. Compounds of claim 4 where Q is##STR196##
 9. Compounds of claim 4 where Q is ##STR197##
 10. Compoundsof claim 4 where Q is ##STR198##
 11. Compounds of claim 4 where Q is##STR199##
 12. Compounds of claim 4 where Q is ##STR200##
 13. Compoundsof claim 4 where Q is ##STR201##
 14. Compounds of claim 4 where Q is##STR202##
 15. Compounds of claim 4 where Q is ##STR203##
 16. Compoundsof claim 4 where Q is ##STR204##
 17. Compounds of claim 4 where Q is##STR205##
 18. Compounds of claim 4 where Q is ##STR206##
 19. Compoundsof claim 4 where Q is ##STR207##
 20. Compounds of claim 4 where Q is##STR208##
 21. Compounds of claim 4 where Q is ##STR209##
 22. Compoundsof claim 4 where Q is ##STR210##
 23. Compounds of claim 4 where Q is##STR211##
 24. Compounds of claim 4 where Q is ##STR212##
 25. Compoundsof claim 4 where Q is ##STR213##
 26. Compounds of claim 4 where Q is##STR214##
 27. Compounds of claim 4 where Q is ##STR215##
 28. Compoundsof claim 4 where Q is ##STR216##
 29. Compounds of claim 4 where Q is##STR217##
 30. A compound of claim 1 which is selected from the groupconsisting ofN-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-aminocarbonyl]-2-(1- and/or2-methyl-1H-pyrazol-3-yl)benzenesulfonamide;N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-(1-methyl-1H-pyrazol-4-yl)benzenesulfonamide;and2-(isoxazol-4-yl)-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]benzenesulfonamide.31. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 1and at least one of the following: surfactant, solid or liquid diluent.32. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 2and at least one of the following: surfactant, solid or liquid diluent.33. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 3and at least one of the following: surfactant, solid or liquid diluent.34. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 4and at least one of the following: surfactant, solid or liquid diluent.35. A method for controlling the growth of undesired vegetation whichcomprises applying to the locus to be protected an effective amount of acompound of claim
 1. 36. A method for controlling the growth ofundesired vegetation which comprises applying to the locus to beprotected an effective amount of a compound of claim
 2. 37. A method forcontrolling the growth of undesired vegetation which comprises applyingto the locus to be protected an effective amount of a compound of claim3.
 38. A method for controlling the growth of undesired vegetation whichcomprises applying to the locus to be protected an effective amount of acompound of claim 4.